A review of functions and mechanisms of clay soil conditioners and catalysts in thermal remediation compared to emerging photo-thermal catalysis.

High temperatures and providing sufficient time for the thermal desorption of persistent organic pollutants (POPs) from contaminated clay soils can lead to intensive energy consumption. Therefore, this article provides a critical review of the potential additives which can improve soil texture and increase the volatility of POPs, and then discusses their enhanced mechanisms for contributing to a green economy. Ca-based additives have been used to reduce plasticity of bentonite clay, absorb water and replenish system heat. In contrast, non-Ca-based additives have been used to decrease the plasticity of kaolin clay. The soil structure and soil plasticity can be changed through cation exchange and flocculation processes. The transition metal oxides and alkali metal oxides can be applied to catalyze and oxidize polycyclic aromatic hydrocarbons, petroleum and emerging contaminants. In this system, reactive oxygen species (•O2- and •OH) are generated from thermal excitation without strong chemical oxidants. Moreover, multiple active ingredients in recycled solid wastes can be controlled to reduce soil plasticity and enhance thermal catalysis. Alternatively, the alkali, nano zero-valent iron and nano-TiN can catalyze hydrodechlorination of POPs under reductive conditions. Especially, photo and photo-thermal catalysis are discussed to accelerate replacement of fossil fuels by renewable energy in thermal remediation.

Mechanisms of heating-electrokinetic co-driven perfluorooctanoic acid (PFOA) adsorption on zeolite.

Slow release of emerging contaminants limits their accessibility from soil to pore water, constraining the treatment efficiency of physio-chemical treatment sites. DC fields mobilize organic contaminants and influence their interactions with geo-matrices such as zeolites. Poor knowledge, however, exists on the joint application of heating and electrokinetic approaches on perfluorooctanoic acid (PFOA) transport in porous media. Here, we investigated electrokinetic PFOA transport in zeolite-filled percolation columns at varying temperatures. Variations of pseudo-second-order kinetic constants (kPSO) were correlated to the liquid viscosity variations (η) and elctroosmotic flow velocities (vEOF). Applying DC fields and elevated temperature significantly (>37%) decreased PFOA sorption to zeolite. A good correlation between η, vEOF, and kPSO was found and used to develop an approach interlinking the three parameters to predict the joint effects of DC fields and temperature on PFOA sorption kinetics. These findings may give rise to future applications for better tailoring PFOA transport in environmental biotechnology.

A novel prediction approach driven by graph representation learning for heavy metal concentrations.

The potential risk of heavy metals (HMs) to public health is an issue of great concern. Early prediction is an effective means to reduce the accumulation of HMs. The current prediction methods rarely take internal correlations between environmental factors into consideration, which negatively affects the accuracy of the prediction model and the interpretability of intrinsic mechanisms. Graph representation learning (GraRL) can simultaneously learn the attribute relationships between environmental factors and graph structural information. Herein, we developed the GraRL-HM method to predict the HM concentrations in soil-rice systems. The method consists of two modules, which are PeTPG and GCN-HM. In PeTPG, a graphic structure was generated using graph representation and communitization technology to explore the correlations and transmission paths of different environmental factors. Subsequently, the GCN-HM model based on the graph convolutional neural network (GCN) was used to predict the HM concentrations. The GraRL-HM method was validated by 2295 sets of data covering 21 environmental factors. The results indicated that the PeTPG model simplified correlation paths between factor nodes from 396 to 184, reducing by 53.5 % graph scale by eliminating the invalid paths. The concise and efficient graph structure enhanced the learning efficiency and representation accuracy of downstream prediction models. The GCN-HM model was superior to the four benchmark models in predicting the HM concentration in the crop, improving R2 by 36.1 %. This study develops a novel approach to improve the prediction accuracy of pollutant accumulation and provides valuable insights into intelligent regulation and planting guidance for heavy metal pollution control.

Feasibility of using Vis-NIR spectroscopy and PXRF spectrometry to estimate regional soil cadmium concentration.

Conventionally, soil cadmium (Cd) measurements in the laboratory are expensive and time-consuming, involving complex processes of sample preparation and chemical analysis. This study aimed to identify the feasibility of using sensor data of visible near-infrared reflectance (Vis-NIR) spectroscopy and portable X-ray fluorescence spectrometry (PXRF) to estimate regional soil Cd concentration in a time- and cost-saving manner. The sensor data of Vis-NIR and PXRF, and Cd concentrations of 128 surface soils from Yunnan Province, China, were measured. Outer-product analysis (OPA) was used for synthesizing the sensor data and Granger-Ramanathan averaging (GRA) was applied to fuse the model results. Artificial neural network (ANN) models were built using Vis-NIR data, PXRF data, and OPA data, respectively. Results showed that: (1) ANN model based on PXRF data performed better than that based on Vis-NIR data for soil Cd estimation; (2) Fusion methods of both OPA and GRA had higher predictive power (R2) = 0.89, ratios of performance to interquartile range (RPIQ) = 4.14, and lower root mean squared error (RMSE) = 0.06, in ANN model based on OPA fusion; R2 = 0.88, RMSE = 0.06, and RPIQ = 3.53 in GRA model) than those based on either Vis-NIR data or PXRF data. In conclusion, there exists a great potential for the combination of OPA fusion and ANN to estimate soil Cd concentration rapidly and accurately.

Structure-dependent degradation of phthalate esters with persulfate oxidation activated by thermal in soil.

Phthalate esters (PAEs) have become one of the most concerned emerging organic pollutants in the world, due to the toxicity to human health, and hard to remove it efficiently. In this study, the degradation performance of DBP and DEHP in the soil by water bath heating activated sodium persulfate (PS) method under different factors were studied, in which the degradation rate of DBP and DEHP were improved with the increasing of temperature, PS concentration and water/soil ratio, and higher diffusion efficiency treatments methods, due to the improved mass transfer from organic phase to aqueous media. However, the degradation rate of DEHP was much lower than that of DBP, because DEHP in the soil was more difficult to contact with SO4•- for reaction on soil surface, and the degradation rate of PAEs in soil was significantly lower than that in water. Redundancy analysis of degradation rate of DBP and DEHP in water demonstrated that the key factors that determine the degradation rate is time for DBP, and cosolvent dosage for DEHP, indicating that the solubility and diffusion rate of PAEs from soil to aqueous are predominance function. This study provides comprehensive scenes in PAEs degradation with persulfate oxidation activated by thermal in soil, reveal the difference of degradation between DBP and DEHP is structure-dependent. So that we provide fundamental understanding and theoretical operation for subsequent filed treatment of various structural emerging pollutants PAEs contaminated soil with thermal activated persulfate.

State of the art in self-sustaining smoldering for remediation of contaminated soil and disposal of organic waste.

Smoldering combustion applications in energy and environmental fields have attracted increasing research attention in recent years. Smoldering has demonstrated considerable green advantages, such as having a low carbon footprint and being sustainable, for remediation of organic-contaminated soil and disposal of high-moisture, low-calorific value, slurry-type organic waste due to its self-sustaining reaction characteristic. This review aims to analyze and summarize studies on smoldering applications to refine the critical components of applied smoldering systems, key reaction characteristics, and corresponding influencing conditions that affect their effectiveness. Furthermore, the common characteristics and influencing factors of different smoldering application scenarios are compared to provide a comprehensive reference for commercial applications. Thus, this paper specifically includes an overview of the impact of inert porous media, combustible material, and oxidants in applied smoldering systems; a review of the research status of the three key reaction characteristics, including peak temperature, smoldering front propagation velocity, and self-sustainability; a summary of typical influencing factors, disposal material characteristics, and control conditions in the two mainstream application directions, which are remediation of contaminated soil and disposal of organic waste; and a comparative analysis of the common modes of applied smoldering beyond the lab scale. As a technically effective and energy-efficient emerging technology, the prospects of smoldering as a robust treatment process in environmental pollution cleanup are presented.

Green mechanochemical activation of solid persulfate to remove PAHs in soil: Performance and mechanism.

Due to the high biotoxicity and persistence of polycyclic aromatic hydrocarbons (PAHs), the remediation of PAHs-contaminated soil becomes an intractable problem. Persulfate-based advanced oxidation processes are widely used to degrade PAHs in aquatic environment. However, they are not convenient for used in soil due to the heterogeneity and complexity of soil matrix. In this study, a green and convenient ball milling process is introduced to activate persulfate for the remediation of PAHs-contaminated soil. About 82.5% PAHs were removed with 10% wt. Na2S2O8 (PS) addition and ball-milling for 2 h under 500 r/min. The degradation of PAHs is attributed to the attack of radicals (SO4·- and·OH) generated from the activation of PS by mechanochemistry. Moreover, stable Si-O bonds were disrupted during ball-milling process, and formed free electron on the surface of soil particles. This facilitates the electron transfer from oxidants to contaminants. The particle size, surface element composition, functional group, and thermogravimetric analysis confirmed the slight disturbance of ball-milling-assisted PS process on the physical and chemical properties of soil. Therefore, ball-milling assisted PS approach would be a promising technology for the remediation of PAHs-contaminated soil.

Effects of Temperature and DC Electric Fields on Perfluorooctanoic Acid Sorption Kinetics to Activated Carbon.

Sorption to activated carbon is a common approach to reducing environmental risks of waterborne perfluorooctanoic acid (PFOA), while effective and flexible approaches to PFOA sorption are needed. Variations in temperature or the use of electrokinetic phenomena (electroosmosis and electromigration) in the presence of external DC electric fields have been shown to alter the contaminant sorption of contaminants. Their role in PFOA sorption, however, remains unclear. Here, we investigated the joint effects of DC electric fields and the temperature on the sorption of PFOA on activated carbon. Temperature-dependent batch and column sorption experiments were performed in the presence and absence of DC fields, and the results were evaluated by using different kinetic sorption models. We found an emerging interplay of DC and temperature on PFOA sorption, which was linked via the liquid viscosity (η) of the electrolyte. For instance, the combined presence of a DC field and low temperature increased the PFOA loading up to 38% in 48 h relative to DC-free controls. We further developed a model that allowed us to predict temperature- and DC field strength-dependent electrokinetic benefits on the drivers of PFOA sorption kinetics (i.e., intraparticle diffusivity and the film mass transfer coefficient). Our insights may give rise to future DC- and temperature-driven applications for PFOA sorption, for instance, in response to fluctuating PFOA concentrations in contaminated water streams.

Heat and mass transfer induced by alternating current during desorption of PAHs from soil using electrical resistance heating.

The transfer of heat and contaminants by alternating current (AC) and the removal mechanism of polycyclic aromatic hydrocarbons (PAHs) in electrical resistance heating (ERH) need further study. The main factors affecting heat transfer and water evaporation in the ERH experiment were studied, and the desorption efficiency, temporal and spatial distribution and kinetic behavior under various conditions were analyzed. The results suggested that moisture content was a necessary condition to ensure effective heating of soil, and soil moisture content above 30% was recommended. Higher voltage intensity and/or ion concentration meant stronger input power, resulting in the rapider heating process and the shorter the boiling time. At a low desorption temperature (about 100°C), the Phe desorption mainly depended on the volatilization of surface Phe and the co-boiling of Phe-water. In ERH, the participation of AC would accelerate the diffusion of pollutants from the internal pores of soil particles and their redistribution with water phase, thus improving the Phe removed by co-boiling. It was noteworthy that AC just greatly promoted solid-liquid mass transfer, but it hardly promoted desorption directly, and the removal still depended on Phe-water co-boiling. The Phe desorption efficiency could be significantly improved from 14.0~18.4% to 59.6~70.8% under the combined action of current strengthening Phe diffusion and co-boiling. Thermogravimetric and product analysis confirmed that no new organic matter was generated, but only Phe entered the gas phase through phase change.

Characteristics of the pyrolytic products and the pollutant emissions at different operating stages from a pilot waste tire pyrolysis furnace.

Pyrolysis is considered a highly practical, cost-effective, and environment-friendly technology for waste tires disposal. In this study, pyrolysis processes of waste tires were conducted in a pilot scale furnace feeding at 30 kg/h. The properties of pyrolytic products and the distribution patterns of pollutants generated in different operating stages (start-up, steady, and shut-down) were investigated. The pyrolytic gas in the steady state had a high caloric value of 10799 kJ/Nm3, valuable as heating source for pyrolysis. The elements of sulfur and zinc were effectively fixed as ZnS in the pyrolytic carbon. The basic properties of pyrolytic oil were in line with commercial diesel oil except for the lower flash point. Heavy metals were mainly concentrated in the pyrolytic carbon, with slightly higher concentrations in the steady state. Moreover, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were mainly concentrated in the pyrolytic oil, with predominated low-ring PAHs and high chlorinated PCDD/Fs. The concentrations of PAHs and PCDD/Fs in the gas phase were higher during the start-up stage due to the memory effect, whereas were effectively reduced during the steady stage. The concentration of PAHs in the solid phase was highest during the furnace start-up and lowest in the shut-down stage. In contrast to PAHs, the PCDD/Fs in the solid phase reached their highest concentration during the shut-down stage, which was mainly affected by temperature. The results provide guidance for the reducing of pollutant emissions and the recycling of pyrolytic products.

Dipole field in nitrogen-enriched carbon nitride with external forces to boost the artificial photosynthesis of hydrogen peroxide.

Artificial photosynthesis is a promising strategy for efficient hydrogen peroxide production, but the poor directional charge transfer from bulk to active sites restricts the overall photocatalytic efficiency. To address this, a new process of dipole field-driven spontaneous polarization in nitrogen-rich triazole-based carbon nitride (C3N5) to harness photogenerated charge kinetics for hydrogen peroxide production is constructed. Here, C3N5 achieves a hydrogen peroxide photosynthesis rate of 3809.5 µmol g-1 h-1 and a 2e- transfer selectivity of 92% under simulated sunlight and ultrasonic forces. This high performance is attributed to the introduction of rich nitrogen active sites of the triazole ring in C3N5, which brings a dipole field. This dipole field induces a spontaneous polarization field to accelerate a rapid directional electron transfer process to nitrogen active sites and therefore induces Pauling-type adsorption of oxygen through an indirect 2e- transfer pathway to form hydrogen peroxide. This innovative concept using a dipole field to harness the migration and transport of photogenerated carriers provides a new route to improve photosynthesis efficiency via structural engineering.

Lab-scale transport and activation of peroxydisulfate for phenanthrene degradation in soil: A comprehensive assessment of the remediation process, soil environment and microbial diversity.

Electrokinetic transport followed by electrical resistance heating activation of peroxydisulfate is a novel in situ soil remediation method. However, the strategy of electrokinetic transport coupled with electrical resistance heating and the comprehensive evaluation of restored soil need to be further explored. In this study, a lab-scale simulation device for in situ electrokinetic transport coupled with electrical resistance heating activation of peroxydisulfate was constructed to monitor the transport and transfer of peroxydisulfate, target pollutants, and process parameters, and the physicochemical properties and bacterial community of treated soil were evaluated. The results showed that adding 10 wt% peroxydisulfate to both the anode and cathode resulted in the optimized transfer rate and cumulative concentration of peroxydisulfate under electrokinetics. After 8 h, the cumulative concentration of peroxydisulfate reached 66.15- 166.29 mmol L-1, which was attributed to the migration of a large amount of S2O82- from the cathode to the soil under electromigration. Additionally, the anodic interfacial electric potential was improved, which was more conducive to electroosmotic transport of peroxydisulfate from the anode chamber. By alternating electrokinetic transport and electrical resistance heating activation of peroxydisulfate for two cycles, the phenanthrene degradation efficiency in four evenly distributed wells between electrodes reached 75.4 %, 87.6 %, 92.3 %, and 94.4 %. With slight variations in soil morphology and structure, the electrokinetic transport coupled with electrical resistance heating activation of peroxydisulfate elevated the soil fertility index. The abundance and diversity of bacterial communities in treated soil recovered to above the original soil level after 15 days. Our findings may support the application of electrokinetic transport coupled with electrical resistance heating activation of peroxydisulfate as a promising green ecological technology for the in situ remediation of organic-contaminated soil.

Synergetic degradation of perfluorooctanoic acid (PFOA) in soil using electrical resistance heating induced persulfate activation.

Due to wastes from production of fluorinated materials and use of aqueous fire-fighting foams (AFFF), soils contaminated with perfluorooctanoic acid (PFOA) is of concern. However, current PFOA-contaminated soil disposal techniques have relatively low degradation efficiencies and are not suitable for on-site remediation. In this study, an electrical resistance heating (ERH) device and a box experimental device were used to study whether ERH induced persulfate activation (ERH/PS) could degrade PFOA in the soil. The results indicated that single ERH and single PS addition could not effectively degrade PFOA (with approximately 0.3 % and 3.9 % degradation after 9 h, respectively), while the degradation efficiency of PFOA with coupled ERH/PS could reach 87.3 % after 9 h of reaction. Moreover, effects of PS content, heating temperature, and soil organic matter on the degradation of PFOA were explored. During the ERH/PS process, PFOA was gradually transformed into short chain perfluorinated compounds and finally mineralized to fluoride ions. Finally, using a box experimental device, PS was effectively transported to the target contaminated area through electrokinetic (EK)-assisted delivery. After activating PS through ERH, the degradation rate of PFOA could reach 95.5 %. This is a novel study demonstrating the feasibility of ERH induced PS activation to degrade PFOA in soil, which provides a potential on-site strategy for remediation of PFOA-contaminated soil.

Ensemble learning-based applied research on heavy metals prediction in a soil-rice system.

Accurate prediction of heavy metal accumulation in soil ecosystems is crucial for maintaining healthy soil environments and ensuring high-quality agricultural products, as well as a challenging scientific task. In this study, we constructed a dataset containing 490 sets of multidimensional environmental covariate data and proposed prediction models for heavy metal concentrations (HMC) in a soil-rice system, EL-HMC (including RF-HMC and GBM-HMC), based on Random Forest (RF) and Gradient Boosting Machine (GBM) ensemble learning (EL) techniques. To reasonably evaluate the effectiveness of each model, Multiple linear and Bayesian regressions were selected as benchmark models (BM), and mean absolute error (MAE), root mean square error (RMSE), and determination coefficient R2 were selected as evaluation indicators. In addition, sensitivity and spatial autocorrelation (SAC) analyses were used to examine the robustness of the model. The results showed that the R2 values of RF-HMC and GBM-HMC for modeling available cadmium (Cd) concentrations in soil were 0.654 and 0.690, respectively, with an average increase of 48.0 % compared to the BMs. The R2 values of RF-HMC and GBM-HMC for predicting Cd, lead (Pb), chromium (Cr), and mercury (Hg) concentrations in rice ranged from 0.618 to 0.824 and 0.645 to 0.850, respectively, with an average increase of 58.2 % compared with the BMs. The corresponding MAEs and RMSEs of RF-HMC and GBM-HMC had low error levels. Sensitivity analysis of the input features and the SAC of the prediction bias showed that the EL-HMC models have excellent robustness. Therefore, the EL technology-based prediction models for HMCs proposed herein are practical and feasible, demonstrating better accuracy and stability than the traditional model. This study verifies the application potential of EL technology in pollution ecology and provides a new perspective and solution for sustainable management and precise prevention of heavy metal pollution in farmland soil at the regional scale.

Fe2O3 micron particles are critical for electron transfer and the distribution of electrochemically active bacteria in soil MFCs.

Fe2O3 plays a complex role in soil electron transfer. A microbial fuel cell (MFC) was constructed to drive the directional transfer of electrons in soil, and the results revealed that Fe2O3 acts first as a capacitor, intercepting and reserving the electrons produced by electrochemically active bacteria (EAB) in the soil, which leads to a decrease in hexachlorobenzene (HCB) removal efficiency with increasing proportions of Fe2O3 dosing (R2 = 0.85). The Fe2O3 then exerted its semiconductor properties in synergy with dissolved Fe2+ as an electron mediator to promote the flow of electrons in the soil. Power generation by the MFC was significantly and positively correlated with the concentration of dissolved Fe2+ (r = 0.51) and the Fe2O3 dosing proportion (r = 0.97). The higher HCB removal efficiency, spatial distribution of intercepted electrons, and abundance of electron transfer metabolic pathways confirmed that Fe2O3 promoted electron-flow fluxes in soil. Additionally, Geobacter sp., (direct electron transfer) and Pseudomonas sp., (indirect electron transfer) were the dominant electrochemically active bacteria in the anode and soil of MFC, respectively. In this study, both dissolved (Fe2+) and solid state (Fe2O3) electron mediators functioned as electron transporters in soil, we propose an internal "electron internet" of soil consisting of points and lines.

Soil physiochemical properties and bacterial community changes under long-term polycyclic aromatic hydrocarbon stress insitu steel plant soils.

In situ soils were collected at two depths in Jinan and Hangzhou steel plants, which both have a long history of operation and polycyclic aromatic hydrocarbons (PAHs) contamination. The richness of 16 S rRNA gene and bacterial community of the soil were determined by real-time PCR and high-throughput sequencing. Soil physicochemical properties, PAHs contamination characteristics, and their interrelationships were also analyzed. In general, the PAHs contamination decreased with increasing soil depths. The physicochemical properties and PAH concentration of soil had synergistic impacts on the composition of the bacterial community. The long-term higher PAHs stress in Hangzhou contaminated soil (982 mg kg-1) increased the bacterial abundance and diversity, while that of Jinan contaminated soil (63 mg kg-1) decreased bacterial abundance and diversity. The pH value, sand content of the soil were positively correlated (P < 0.05) with the bacterial diversity including Simpson, Shannon, Observed_species and Chao1 indexes., and the other soil properties exhibited negative correlations with different strengths. The abundances of Curvibacter, Pseudomonas, Thiobacillus, Lysobacter, and Limnobacter were positively correlated with the PAHs concentration (P < 0.01). Additionally, the network structure of the PAHs-contaminated soils was more complex compared to that of uncontaminated soils, with stronger linkages and correlations between the different bacteria. These findings provide a theoretical basis for microbial remediation of PAHs-polluted soil.

Role of direct current on thermal activated peroxydisulfate to degrade phenanthrene in soil: Conversion of sulfate radical and hydroxyl radical to singlet oxygen, accelerated degradation rate and reduced efficiency.

Electrokinetic (EK) delivery followed by thermal activated peroxydisulfate (PS) has turned out to be a potential in situ chemical oxidation technology for soil remediation, but the activation behavior of PS in an electrical coupled thermal environment and the effect of direct current (DC) intervention on PS in heating soil has not been explored. In this paper, a DC coupled thermal activated PS (DC-heat/PS) system was constructed to degrade Phenanthrene (Phe) in soil. The results indicated that DC could force PS to migrate in soil, changing the degradation rate-limiting step in heat/PS system from PS diffusion to PS decomposition, which greatly accelerated the degradation rate. In DC/PS system, 1O2 was the only reactive species directly detected at platinum (Pt)-anode, confirming that S2O82- could not directly obtain electrons at the Pt-cathode to decompose into SO4•-. By comparing DC/PS and DC-heat/PS system, it was found that DC could significantly promote the conversion of SO4•- and •OH generated by thermal activation of PS to 1O2, which was attributed to the hydrogen evolution caused by DC that destroys the reaction balance in system. It was also the fundamental reason that DC leaded to the reduction of oxidation capacity of DC-heat/PS system. Finally, the possible degradation pathways of phenanthrene were proposed on the basis of seven detected intermediates.

Enhanced Adsorption of Sulfonamides by Attapulgite-Doped Biochar Prepared with Calcination.

The extensive use of sulfonamides seriously threatens the safety and stability of the ecological environment. Developing green inexpensive and effective adsorbents is critically needed for the elimination of sulfonamides from wastewater. The non-modified biochar exhibited limited adsorption capacity for sulfonamides. In this study, the attapulgite-doped biochar adsorbent (ATP/BC) was produced from attapulgite and rice straw by calcination. Compared with non-modified biochar, the specific surface area of ATP/BC increased by 73.53−131.26%, and the average pore width of ATP/BC decreased 1.77−3.60 nm. The removal rates of sulfadiazine and sulfamethazine by ATP/BC were 98.63% and 98.24%, respectively, at the mass ratio of ATP to rice straw = 1:10, time = 4 h, dosage = 2 g∙L−1, pH = 5, initial concentration = 1 mg∙L−1, and temperature = 20 °C. A pseudo-second-order kinetic model (R2 = 0.99) and the Freundlich isothermal model (R2 = 0.99) well described the process of sulfonamide adsorption on ATP/BC. Thermodynamic calculations showed that the adsorption behavior of sulfonamides on the ATP/BC was an endothermic (ΔH > 0), random (ΔS > 0), spontaneous reaction (ΔG < 0) that was dominated by chemisorption (−20 kJ∙mol−1 > ΔG). The potential adsorption mechanisms include electrostatic interaction, hydrogen bonding, π−π interaction, and Lewis acid−base interactions. This study provides an optional material to treat sulfonamides in wastewater and groundwater.

Revealing the Mechanism of Dioxin Formation from Municipal Solid Waste Gasification in a Reducing Atmosphere.

Gasification is an effective technology for the thermal disposal of municipal solid waste (MSW) with lower dioxin emission compared to the prevailing incineration process. Nevertheless, the mechanism of dioxin formation in the reducing atmosphere during the gasification process was seldomly explored. Herein, the effects of the atmosphere, temperature, and chlorine source were systematically investigated in terms of dioxin distribution. With CO2 and H2O as gasification agents, a reducing reaction atmosphere was formed with abundant H2 which effectively suppressed the generation of C-Cl, contributing to a substantial decrease of dioxin concentration by ∼80% compared to the incineration process. The formation of dioxin was favored at temperatures below 700 °C with its peak concentration achieved at 500 °C. It was unveiled that inorganic chlorine played a dominant role in the reducing atmosphere, with a lower proportion of C-O-C/O-C═O on residual slag compared to an oxidizing atmosphere. Additionally, the generated H2 reduced the concentration of dioxins by attacking C-Cl and inhibiting the crucial Deacon reaction for dioxin formation, validated by density functional theory calculation. Eventually, the formation route paradigm and the reaction mechanism of dioxin formation from MSW gasification were revealed, facilitating and rationally guiding the control of dioxin emission.

Spatial Distribution and Assessment of the Human Health Risks of Heavy Metals in a Retired Pharmaceutical Industrial Area, Southwest China.

Heavy metals pollution in pharmaceutical industries received increasing attention. A total of 94 soil samples were collected in this study. Results showed the mean contents of Hg, Cd, As, Pb, Ni and Cu were 0.21, 0.26, 9.59, 55.06, 51.52 and 50.81 mg·kg-1, respectively. The spatial distribution of metals in topsoil largely attributed to the pharmaceutical production process. The distribution of Hg and As were related to the production of medical absorbent cotton. While Ni was related to the fuel supply of Ni-rich coal. Cr, Cu and Pb mainly distributed in the process which they were used as catalysts. The vertical migration of metals was complex in soil. To a great extent, it was related to the texture of the soil and the properties of metals in this filed. The total non-cancer and cancer human health risk were within the limits of USEPA (10-6 a-1). This demonstrated the health risks of individual's exposure to heavy metals in this factory was acceptable.