Migration and morphological transformation patterns of heavy metals on sludge cells and extracellular polymeric substances (EPS) under the influence of different treatments.

The impediment of sludge resource utilization stems from the presence of heavy metals within the sludge matrix. To optimize heavy metal removal techniques from undried sludge, it is essential to study the distribution of heavy metals in the sludge flocs structure and the changes in morphology in the sludge cells after different treatments. In this study, the sludge was subjected to chemical treatments using citric acid (CA), EDTA, and saponin, as well as electrokinetic treatment at 2 V/cm. The distribution and migration of Cu, Ni, and Zn in sludge flocs after various treatment methods were analyzed. The heavy metals were found to migrate from intracellular to extracellular polymeric substances (EPS) without causing extensive sludge cell lysis. They gradually diffused outward with the dispersion of the EPS layer. The migration efficiency of the three heavy metals in the sludge flocs was Zn, Ni, and Cu. This was mainly related to the initial distribution and morphology of the heavy metals. Under the influence of chemicals and an electric field, the acid-soluble and reducible heavy metals in the cells partially migrated to the EPS, while the stable heavy metals transformed into an unstable state. Furthermore, the order of chemical reagents in terms of their effect on the migration efficiency of heavy metals was CA > EDTA > Saponin, owing to the varying binding strengths of heavy metals and their impact on the degree of loosening of the EPS. Especially after CA treatment a greater proportion of Cu, Ni, and Zn were transferred from the cells to the EPS. The acidification effect near the anode during electrokinetic treatment intensifies the migration of heavy metals. This study provides basic research for subsequent engineering optimization aimed at removing heavy metals from sludge.

New-style electrokinetic-adsorption remediation of cadmium-contaminated soil using double-group electrodes coupled with chitosan-activated carbon composite membranes.

Global soil cadmium (Cd(II)) contamination threatens the soil environment, food safety, and human health. Conventional electrokinetic remediation (EKR) and enhancement methods usually operate in strong electric fields, leading to strong side reactions and uneven removal. In this work, to remove Cd(II) from soil effectively in a low-voltage electric field, a new-style electrokinetic-adsorption remediation using double-group electrodes coupled with chitosan-activated carbon composite membranes (DE-EKR-CAC) was developed. Chitosan-activated carbon (CAC) composite membranes were synthesized for easy recovery and reuse of adsorbents. The effects of pH, contact time, initial concentration, and foreign ions on the removal of Cd(II) by the CAC composite membranes were determined. The CAC composite membranes performed well except in a strongly acidic environment (pH = 2.0). The soil pH varied between 3.4 and 5.0 in DE-EKR-CAC, where the CAC composite membranes were applicable. High concentrations of Ca2+ interfered with the adsorption of Cd(II), which means that the selectivity of CAC composite membranes for Cd(II) is not high enough. The Langmuir (R2 = 0.999) and pseudo-second-order kinetic (R2 = 1.0) models revealed the monolayer coverage and chemisorption mechanism, and the maximum adsorption capacity was 40.81 mg/g. Furthermore, SEM, FTIR, and XPS analyses suggest that physical adsorption, complexation of oxygen-containing functional groups, chelation of amino groups, and ion exchange are potential mechanisms for the adsorption of Cd(II) on CAC. DE-EKR-CAC performed better than the group remediated with one set of electrodes, with higher removal efficiencies and more uniform removal. The lowest energy consumption was 3.33 kWh/m3, which is lower than other enhancement methods. Separation of CAC composite membranes from soil is easy, and reuse performance is good. DE-EKR-CAC provides a potential option for Cd(II) removal from soil because of its better performance using low-voltage direct current, low energy consumption, and ease of recycling the adsorbent.

Electrokinetic remediation for the removal of heavy metals in soil: Limitations, solutions and prospection.

Electrokinetic remediation (EKR) technology is a promising method to remove heavy metals from low permeability soil, because it is environmentally friendly, efficient and economical, and can realize in-situ remediation. In this paper, the basic principles and related physical and chemical phenomena of EKR are systematically summarized, and three limiting problems of EKR technology are put forward: the weak ability of dissolving metals, focusing effect, and energy consumption. There are many methods to solve these technical problems, but there is a lack of systematic summary of the causes of problems and solutions. Based on various enhanced EKR technologies, this paper summarizes the main ideas to solve the limiting problems. The advantages and disadvantages of each technology are compared, which has guiding significance for the development of new technology in the future. This paper also discusses the dissolution of residual heavy metals, which is rare in other articles. The energy consumption of EKR and the remediation effect are equally important, and both can be used as indicators for evaluating the feasibility of new technologies. This paper reviews the influence of various electric field conditions on power consumption, such as renewable energy supply, new electrode materials and electrode configurations, suitable voltage values and functional electrolytes. In addition, a variety of energy consumption calculation methods are also introduced, which are suitable for ohmic heat loss, energy distribution when there is non-target ion competition, and power consumption of specific ions in various metal ions. Researchers can make selective reference according to their actual situations. This paper also systematically introduces the engineering design and cost calculation of EKR, lists the research progress of some engineering cases and pilot-scale tests, analyzes the reasons why it is difficult to apply EKR technology in large-scale engineering at present, and puts forward the future research direction.

Synthesis of Hierarchical-Porous Fluorinated Metal-Organic Frameworks with Superior Toluene Adsorption Properties.

Constructing metal-organic frameworks (MOFs) with high volatile organic compounds (VOCs) adsorption capacity and excellent water resistance remain challenging. Herein, a monocarboxylic acid-assisted mixed ligands strategy was designed to synthesize a novel fluorinated MOFs, MIL-53 (Al). The monocarboxylic acid promoted crystallization and produced abundant crystal defects, which increased pore volume. Moreover, the competitive coordination between tetrafluoroterephthalic acid and 1,4-dicarboxybenzene was moderated by monocarboxylic modulators, significantly improving the hydrophobicity. The toluene uptake of the optimal sample reached 254.85 mg g-1 under humid conditions, increased by 33.56 % of MIL-53(Al), and the QWet /QDry (the ratio of adsorption quality under wet to adsorption quality under dry) was 0.92, remarkably surpassing that of origin MIL-53 (0.72). The recycle experiment showed superior reusability with no performance degradation after 10 recycle under RH=50 % (relative humidity). The adsorptive kinetic and thermodynamic analysis proves that the adsorption process is controlled by surface mono-layer adsorption and pore diffusion. The fluorine group affects the internal diffusion, which weakens the transfer rate. This strategy opens a new prospect of obtaining hierarchical functional MOFs for meeting the VOCs uptake under the practical application.

Recent Advances of Chlorinated Volatile Organic Compounds' Oxidation Catalyzed by Multiple Catalysts: Reasonable Adjustment of Acidity and Redox Properties.

The severe hazard of chlorinated volatile organic compounds (CVOCs) to human health and the natural environment makes their abatement technology a key topic of global environmental research. Due to the existence of Cl, the byproducts of CVOCs in the catalytic combustion process are complex and toxic, and the possible generation of dioxin becomes a potential risk to the environment. Well-qualified CVOC catalysts should process favorable low-temperature catalytic oxidation ability, excellent selectivity, and good resistance to poisoning, which are governed by the reasonable adjustment of acidity and redox properties. This review overviews the application of different types of multicomponent catalysts, that is, supported noble metal catalysts, transition metal oxide/zeolite catalysts, composite transition metal oxide catalysts, and acid-modified catalysts, for CVOC degradation from the perspective of balance between acidity and redox properties. This review also highlights the synergistic degradation of CVOCs and NOx from the perspective of acidity and redox properties. We expect this work to inspire and guide researchers from both the academic and industrial communities and help pave the way for breakthroughs in fundamental research and industrial applications in this field.

Effects of Three Sludge Products from Co-Treatment of Wastewater on the Soil Properties and Plant Growth of Silty Loam.

Currently, little is known about systematic comparisons of sludge products obtained from different sludge treatment processes in terms of land use. Moreover, it is worth evaluating whether the sludge produced from the co-treatment of industrial wastewater and domestic sewage can be applied to land use. In this study, three sludge products derived from the same municipal sludge-sludge biochar (SSB), dried sludge (DSS), and sludge compost (SSC)-were added to silty loam (SL) at a 20% mass ratio to assess their effects on soil structure, properties, and fertility. Chinese cabbage was planted as a model crop and its growth and physiological state were monitored. The experimental results showed that the water retention of the soil was significantly related to its porosity, and the moisture in the three sludge products-modified soil mainly existed in the form of free water. The addition of three sludge products increased the total porosity of SL. SSC enhanced the water retention of SL by increasing the capillary porosity, and SSB improved the gas permeability of SL by increasing the non-capillary porosity. The three sludge products all increased the content of large particles in the soil and improved the stability of the aggregates of SL. Among them, SSB and DSS had significant effects on improving the stability of the aggregates. Although the addition of the three sludge products improved the fertility of SL, compared with that of DSS and SSC, the addition of SSB made the growth indices of Chinese cabbage the best, indicating that SSB can effectively maintain soil nutrients. The heavy metal test results of Ni showed that SSB had a good stabilizing effect on heavy metals. Therefore, compared with drying and composting, pyrolysis of municipal sludge is more suitable for SL improvement.

In situ removal of cadmium by short-distance migration under the action of a low-voltage electric field and granular activated carbon.

Cd pollution in soil is a global environmental issue of great concern. The secondary release and low removal rate of Cd are obstacles to the use of adsorption techniques. To develop a sustainable and effective remediation technique, low-voltage direct current (DC) and granular activated carbon (GAC) were applied for in situ Cd removal. The results showed that a low-voltage gradient was more favourable than a high-voltage gradient for Cd removal. A voltage gradient of 0.2 V cm-1 acted as a driving force for Cd migration while limiting the side effects caused by DC. As an auxiliary enhancement measure, polarity exchange was effective in maintaining uniform distributions of soil moisture and temperature as well as a stable pH while improving Cd removal by weakening inhibition caused by OH- generated at the cathodes. The average removal rates of total and bioavailable Cd were 61.05% and 76.96%, respectively. The potential mobility of Cd in soil was assessed by the mobility factor (MF). The MF was lowered from 42.66% to 8.96%, indicating that the risks of Cd mobility were reduced to low levels. The energy consumption and utilization efficiency of the method were 5.65 KWh m-3 and 11.25, respectively. The energy utilization efficiency was significantly higher than the efficiencies of other methods that use DC to improve Cd removal. The results suggested that the in situ removal of Cd by low-voltage DC and GAC was efficient and avoided the secondary release of Cd.

Interface-Enhanced Oxygen Vacancies of CoCuOx Catalysts In Situ Grown on Monolithic Cu Foam for VOC Catalytic Oxidation.

The development of highly efficient and stable monolithic catalysts is essential for the removal of volatile organic compounds (VOCs). Copper foam (CF) is a potential ideal carrier for monolithic catalysts, but its low surface area is not conducive to dispersion of active species, thus reducing the interface interaction with active species. Herein, a vertically oriented Cu(OH)2 nanorod was in situ grown on the CF, which acted as the template and precursor to synthesize CoCu-MOF. The optimized catalyst (12CoCu-R) delivers excellent performance for acetone oxidation with a T90 of 195 °C. Impressively, the catalyst demonstrated satisfactory stability in long-term, cycle, water resistance, and high airspeed tests. Therefore, the present study provides a novel strategy for rationally designing efficient monolithic catalysts for VOC oxidation and other environmental applications.

Potential applications of porous organic polymers as adsorbent for the adsorption of volatile organic compounds.

Volatile organic compounds (VOCs) with high toxicity and carcinogenicity are emitted from kinds of industries, which endanger human health and the environment. Adsorption is a promising method for the treatment of VOCs due to its low cost and high efficiency. In recent years, activated carbons, zeolites, and mesoporous materials are widely used to remove VOCs because of their high specific surface area and abundant porosity. However, the hydrophilic nature and low desorption rate of those materials limit their commercial application. Furthermore, the adsorption capacities of VOCs still need to be improved. Porous organic polymers (POPs) with extremely high porosity, structural diversity, and hydrophobic have been considered as one of the most promising candidates for VOCs adsorption. This review generalized the superiority of POPs for VOCs adsorption compared to other porous materials and summarized the studies of VOCs adsorption on different types of POPs. Moreover, the mechanism of competitive adsorption between water and VOCs on the POPs was discussed. Finally, a concise outlook for utilizing POPs for VOCs adsorption was discussed, noting areas in which further work is needed to develop the next-generation POPs for practical applications.

Defective Ultrafine MnOx Nanoparticles Confined within a Carbon Matrix for Low-Temperature Oxidation of Volatile Organic Compounds.

The development of catalysts for volatile organic compound (VOC) treatment by catalytic oxidation is of great significance to improve the atmospheric environment. Size-effect and oxygen vacancy engineering are effective strategies for designing high-efficiency heterogeneous catalysts. Herein, we explored the in situ carbon-confinement-oxidation method to synthesize ultrafine MnOx nanoparticles with adequately exposed defects. They exhibited an outstanding catalytic performance with a T90 of 167 °C for acetone oxidation, which is 73 °C lower than that of bulk MnOx (240 °C). This excellent catalytic activity was primarily ascribed to their high surface area, rich oxygen vacancies, abundant active oxygen species, and good reducibility at low temperatures. Importantly, the synthesized ultrafine MnOx exhibited impressive stability in long-term, cycling and water-resistance tests. Moreover, the possible mechanism for acetone oxidation over MnOx-NA was revealed. In this work, we not only prepared a promising material for removing VOCs but also provided a new strategy for the rational design of ultrafine nanoparticles with abundant defects.

Synthesis of Silanol-Rich MCM-48 with Mixed Surfactants and Their Application in Acetone Adsorption: Equilibrium, Kinetic, and Thermodynamic Studies.

Mesoporous silica MCM-48 with rich silanol was prepared using polyvinylpyrrolidone (PVP) and cetyltrimethylammonium bromide (CTAB) as mixed templates, and the dynamic adsorption performance of acetone was evaluated by testing breakthrough curves. The mixed micelle formed by CTAB and PVP, as well as the hydrogen bond between the carbonyl group of PVP and silanol group affected the condensation process of Si-OH group during the formation of mesoporous structure, resulting in the increase of Si-OH group number on the surface of MCM-48. Compared with MCM-48 synthesized by single template (CTAB), the acetone adsorption capacity of MCM-48 (1:3) synthesized by mixed templates (PVP:CTAB = 1:3) improved by 23.86%, which was attributed to the increase of silanol group amount and the decrease of pore size. In addition, Bangham model had the highest goodness of fit to describe the adsorption process among four kinetic models for the adsorbents, conforming to the mechanism of pore diffusion. The Langmuir and Freundlich models were used to fit the adsorption isotherm data, and the Freundlich model could better describe the adsorption of acetone. Freundlich model fitting results showed that MCM-48 with rich silanol had a strong affinity for acetone, and the adsorption of acetone on MCM-48 belonged to multilayer adsorption. The thermodynamic results showed that the adsorption of MCM-48 for acetone was physical adsorption, and the adsorption behavior was exothermic. This work provided insight into how the inherent properties of an adsorbent and environmental factors (including initial concentration and adsorption temperature) affected the adsorption performance of ketones, thus more ideas could be provided for the accurate design of adsorbents. Furthermore, silanol-rich MCM-48 synthesized by mixed templates is expected to be a promising adsorbent for acetone removal.

Enhanced Acetone Oxidation over the CeO2/Co3O4 Catalyst Derived from Metal-Organic Frameworks.

A novel CeO2/Co3O4 catalyst with a high catalytic activity has been designed and prepared by pyrolysis of metal-organic frameworks, and its catalytic performance was evaluated by the acetone catalytic oxidation reaction. The Co3O4-M catalyst with T90 at 194 °C was prepared by pyrolysis of the MOF-71 precursor, which was 56 °C lower than that of commercial Co3O4 (250 °C). By the addition of cerium to the MOF-71 precursor, an enhanced CeO2/Co3O4 catalyst with T90 at 180 °C was prepared. Importantly, the CeO2/Co3O4 catalyst exhibited superior stability for acetone oxidation. After 10 cycle tests, the conversion could also be maintained at 97% for at least 100 h with slight activity loss. Characterization studies were used to investigate the influence of cerium doping on the property of the catalyst. The results showed that addition of cerium could facilitate the expansion of the surface area and enhance the porous structure and reducibility at low temperature. Furthermore, the surface ratio of Co3+/Co2+ and mobile oxygen obviously improved with the addition of cerium. Therefore, the metal oxides prepared by this method have potential for the elimination of acetone.

Enhanced catalytic performance for volatile organic compound oxidation over in-situ growth of MnOx on Co3O4 nanowire.

Hierarchical Co3O4@MnOx material has been synthesized by in-suit growth of MnOx on the Co3O4 and applied in catalytic oxidation of volatile organic compounds (VOCs). Results revealed that T90 of acetone on the Co3O4@MnOx was 195 °C, which was 36 °C and 32 °C lower than that on the Co3O4 and MnOx/Co3O4, respectively. The universality experiments demonstrated that T90 of ethyl acetate and toluene on the Co3O4@MnOx were 200 °C and 222 °C, respectively. The above results indicated that Co3O4@MnOx catalyst presented a robust catalytic performance. Characterization results showed that high catalytic activity of the Co3O4@MnOx catalyst could be attributed to the improvement of low temperature reducibility, the enhancement of Co3+ and adsorbed oxygen species resulted from the sufficient reaction between MnO4- and Co2+ during secondary hydrothermal process. Furthermore, stability and water-resistance experiments showed the Co3O4@MnOx catalyst with high cycle and long-term stability, satisfied endurability to 5.5-10 vol. % water vapor at 210 °C.

Synthesis of zeolite SSZ-13 from coal gangue via ultrasonic pretreatment combined with hydrothermal growth method.

SSZ-13 zeolite has been widely used in catalysis and adsorption because of good hydrothermal stability and pore structure. However, long crystallization time is the main challenge limiting its industry application. As increased emissions and ineffective treatment, coal gangue not only occupies land, but also pollutes the waterbody and farmland. Using coal gangue as raw material to synthetize zeolite has been considered as an environmentally friendly and effective alternative to solve the issues of accumulation and pollution, which also improves the added value of coal gangue. The ultrasonic assistance has been proven to be one of the potential pretreatment methods to promote the dissolution of crystalline silicon aluminum and reduce the crystallization time of molecular sieve. In this work, SSZ-13 was synthesized by coal gangue via ultrasonic pretreatment combined with hydrothermal growth method. The ultrasonic frequency and power were 20 kHz and 120 W, respectively. The synthesized samples were characterized by XRD, SEM, EDS, BET. The results showed that the crystallization time was shorten to 18 h, which was about 12 h lower than the same conditions of conventional chemicals synthesis. Furthermore, the specific surface area of the synthesized sample was more than 620 m2/g, which also indicated over 95% NOx conversion across a broad range from 180 to 400 °C and over 94% NOx conversion at 200-400 °C after hydrothermal treatment 6 h. This study provides a reference for the environmentally friendly utilization of coal gangue and the low-cost rapid synthesis and application of SSZ-13.

Enhanced catalytic performance for VOCs oxidation on the CoAlO oxides by KMnO4 doped on facile synthesis.

The MnOx was immobilized on the CoAl mixed oxides (CoAlO) derived from hydrotalcites with various anions (CO32-, Cl-, NO3- and SO42-) using the hydration and impregnation methods. The CoAlO oxides modified by KMnO4 were calcined in air at 300 °C to obtain stable oxides, which could be used as catalysts for VOCs (acetone and ethyl acetate) oxidation. CoAlO with CO32- and 30 h of hydration time (CoAlO-C-Mn-30) exhibited a promising catalytic activity (T90 = 173 °C for acetone oxidation; T90 = 175 °C for ethyl acetate), highly superior to CoAlO without KMnO4 modification. The improvement in acetone and ethyl acetate catalytic oxidation was ascribed to the Co3+ and surface adsorbed oxygen species. The increase of Co3+ in the CoAlO-C-Mn-30 oxide thanked to the self-decomposition of KMnO4 and reducibility of Co2+ in the CoAlO oxide during the hydration process. This was also confirmed by XRD and XPS characterization, which showed that Mn cations were enriched on the catalyst surface in the valences of +3 and +4. The catalytic activity of the catalyst remained unchanged in four cycles in the presence of 5.5 vol.% water vapor, which indicated a great potential for industrial application.

Application of weak ultrasonic treatment on sludge electro-osmosis dewatering.

Ultrasonic treatment is a good method of facilitating sewage sludge dewatering characteristics. It can also promote the potential of sludge electro-osmosis dewatering (EDW), which is an accepted method of deep dewatering, but the treatment method and optimizing conditions should be determined by performing experiments. In this study, we consider two treating methods: ultrasonic pre-treatment, which uses ultrasonic treatment as sludge pre-treatment before electro-osmosis dehydration, and ultrasonic coupling, which uses ultrasonic and electric fields simultaneously. Using sludge from the Tianjin Jizhuangzi sewage treatment plant, we analyze the influence of ultrasonic intensity and treatment time on sludge dewatering by performing two different methods. The results show that they effectively facilitated sludge EDW. Under the same conditions, i.e. 2 cm cake initial thickness, voltage of 60 V for 5 min, and 0.1 MPa mechanical pressure for 5.5 min, the optimum processing conditions for ultrasonic pre-treatment were found to be 0.510 W/cm2 and 3.5 min, the dehydration rate reached 34.71%, and the optimum conditions for ultrasonic coupling were 0.255 W/cm2 and 3.5 min, while the dehydration rate reached 40.78%. The dehydration rates for both approaches were clearly better than 17.40%, which was obtained under pure electro-osmosis dehydration. To compare the effects of ultrasonic pre-treatment and ultrasonic coupling on the electro-osmosis dehydration process, in this paper, we present the curves of dehydration rate, electric current, electro-osmosis flow, and scanning electron microscopy for dewatered sludge. Compared with the ultrasonic pre-treatment method, the effect of ultrasonic coupling on electro-osmosis dehydration was more obvious.

Supercritical water pyrolysis of sewage sludge.

Municipal sewage sludge (SS) from wastewater treatment plant containing high water content (>85wt.%), lead to the difficulty of co-combustion with MSW or coal due to the high cost of drying. This study explores an alternative method by supercritical water (SCW) pyrolysis of sewage sludge (SS) in a high pressure reaction vessel. The effects of temperature and moisture content of SS on yield and composition of the products (bio-oil, bio char and non-condensable gas) were studied. A temperature of 385°C and moisture content of 85wt.% were found to be the optimum conditions for the maximum bio-oil production of 37.23wt.%, with a higher heating value of 31.08MJ/kg. In the optimum condition, the yields of aliphatic hydrocarbon and phenols were about 29.23wt.% and 12.51wt.%, respectively. The physical and chemical properties of bio-char were analyzed by using XRF and BET. Results of GC analyses of NCG showed that it has the maximum HHV of 13.39MJ/m3 at 445°C and moisture content of 85wt.%. The reaction path from SS to bio-oil through SCW pyrolysis was given. Moreover, carbon balance was calculated for the optimal condition, and finding out that 64.27wt.% of the carbon content was transferred from SS to bio-oil. Finally, this work demonstrates that the SCW pyrolysis is a promising disposal method for SS.

Drying characteristics of electro-osmosis dewatered sludge.

Electro-osmotic dewatering (EDW) is one of the effective deeply dewatering technologies that is suitable for treating sludge with 55-80% of moisture content. Regarding EDW as the pre-treatment process of drying or incinerating, this article investigated the drying characteristics of electro-osmosis-dewatered sludge, including shear stress test, drying curves analysis, model analysis, and energy balance calculation. After EDW pre-treatment, sludge adhesion was reduced. The sludge drying rate was higher compared to the non-pre-treated sludge, especially under high temperatures (80-120°C). In addition, it is better to place the sludge cake with cathode surface facing upward for improving the drying rate. An adjusted model based on the Logarithmic model could better describe the EDW sludge drying process. Using the energy balance calculation, EDW can save the energy consumed in the process of sludge incineration and electricity generation and enable the system to run without extra energy input.

DEHP enrichment in the surface microlayer of a small eutrophic lake.

Investigation of di-2-ethylhexyl phthalate (DEHP) in the surface microlayer (SM) and subsurface water (SSW) of a small eutrophic lake was carried out from April to June 2002. Results obtained from the field samples showed that tens to several hundred mug/L of DEHP was found in each sample of SM and SSW, indicating that the lake has been polluted by DEHP. Linear regression analysis showed that concentrations of DEHP were more strongly correlated with sampling temperature than with chlorophyll a concentrations. Correlation between DEHP concentrations and total phosphor concentrations was also obtained. Enrichment factors (EFs) of DEHP in the SM comparing with the corresponding SSW were ranging over 0.85-2.12 with an average of 1.35. DEHP EFs were significantly related to both enrichment of chlorophyll a in the SM and sampling temperature.