A bimetallic MOF-derived MnCo spinel oxide catalyst to enhance toluene catalytic degradation.

MnCo spinel oxide catalysts were successfully synthesized by the calcination of bimetallic Mn/Co-MOFs as sacrificial templates. The derived catalysts exhibited optimal catalytic activity, reusability and thermal stability for toluene oxidation, which was ascribed to their large specific surface area, higher number of octahedral metal ions and the weakest metal-oxygen bonds.

Effects of building envelope features on airflow and pollutant dispersion within a symmetric street canyon.

Building envelope features (BEFs) have attracted more and more attention as they have a significant impact on flow structure and pollutant dispersion within street canyons. This paper conducted CFD numerical models validated by wind-tunnel experiments, to explore the effects of the BEFs on characteristics of the airflow and pollutant distribution inside a symmetric street canyon under perpendicular incoming flow. Three different BEFs (balconies, overhangs, and wing walls) and their locations and continuity/discontinuity structures were considered. For each canyon with various BEFs, the air exchange rate (ACH), airflow patterns, and pollutant distributions were evaluated and compared in detail. The results show that compared to the regular canyon, the BEFs will reduce the ACH of the canyon, but increase the disturbances (the proportion of ACH') inside the canyon. The BEFs on the leeward wall have the least influence on the in-canyon airflow and pollutant distributions, followed by that on the windward wall. Then when the BEFs are on both walls, the ventilation capacity of the canyon is weakened greatly, and the pollutant concentration in the ground center is increased significantly, especially near the windward side. Moreover, the discontinuity BEFs will weaken the effect of the continuity BEFs on the in-canyon flow and dispersion, specifically, the discontinuity BEFs reduced the region of high pollutant concentration distributions. These findings can help optimize the BEFs design to enhance ventilation and mitigate traffic pollution.

Fluorination modification enhanced the water resistance of Universitetet i Oslo-67 for multiple volatile organic compounds adsorption under high humidity conditions: Mechanism study.

The construction of metal-organic frameworks (MOFs) with highly efficient capture for volatile organic compounds (VOCs) adsorption under humid conditions is a significant yet formidable task. Herein, series of fluorinated UiO-67 modified with trifluoroacetic acid (TFA) and 4-fluorobenzoic acid were successfully synthesized for VOCs adsorption under high humidity conditions. Experiments results showed that UiO-67 modified with 4-fluorobenzoic acid (67-F) presented excellent adsorption capacity of 345 mg/g for toluene adsorption and exhibited great water resistance (10.0 vol% H2O, 374 mg/g toluene adsorption capacity). Characterization results indicated that the introduction of 4-fluorobenzoic acid induced the competitive coordination between 4-fluorobenzoic acid and 4,4-biphenyl dicarboxylic acid (BPDC) with Zr4+, causing the formation of abundant defects to provide extra adsorption sites. Meanwhile, the benzene ring in 4-fluorobenzoic acid enhanced the π-π conjugation, causing the further promotion of VOCs adsorption capacity. More importantly, the water resistance mechanism was investigated and elucidated that the introduction of F decreased the surface energy of 67-F and its affinity with water. Meanwhile, the metal complex induced by the fluorinated modification produced an electron-dense pore environment, which greatly improved its chemical and water stability. This work provided a strategy for preparing an adsorbent with high water resistance for real-world VOCs adsorption at high humidity conditions.

An essential update on the inventory of landslides triggered by the Jiuzhaigou Mw6.5 earthquake in China on 8 August 2017, with their spatial distribution analyses.

On August 8, 2017, a magnitude Mw6.5 (Ms7.0) earthquake occurred in Jiuzhaigou County, Aba Prefecture, in the northern part of Sichuan Province, China, with a focal depth of 20 km and an epicenter located at (33.2°N, 103.8°E). Due to the significant magnitude of the earthquake, a large number of coseismic landslides were triggered. Despite previous research conducted by experts on the landslides caused by the Jiuzhaigou earthquake, the actual number of landslides has been severely underestimated in the previously published papers. Through field surveys and visual interpretation of high-resolution remote sensing images before and after the mainshock, we have established a detailed inventory of earthquake-induced landslides. The results indicate that the event caused a minimum of 9428 landslides covering a total area of 18.82 km2. These landslides are mainly distributed in the IX intensity area of the earthquake. The landslides mainly consist of medium-sized landslides and debris flows. They predominantly occur in areas with an altitude ranging from 2600 m to 3600 m, with slopes greater than 30° and facing east and southeast. The Lower Carboniferous and Middle Carboniferous formations are more prone to triggering landslides, and landslides are more concentrated within 1 km of roads and in forested areas. Additionally, as the distance from roads and the epicenter increases, the values of LAP and LND decrease, indicating a positive correlation between the two. There are more landslides within 2 km from the fault and within a range of 6 km-9 km from the epicenter. In conclusion, this study provides a comprehensive landslide inventory with broader coverage and increased accuracy. It also conducts a comprehensive analysis of the spatial distribution patterns of landslides. This contributes to a deeper understanding of the causes of coseismic landslides and further research on the impact of landslides in affected areas.

Newly Generated Ca-Feldspar during Sintering Processes Enhances the Mechanical Strength of Coal Gangue-Based Insulation Bricks.

Coal gangue is a solid waste with low carbon content discharged during the course of the coal mining process. The resource utilization of coal gangue could solve environmental problems caused by its excessive production, such as soil contamination and land occupation. This study proposed to produce high-strength thermal insulation bricks using coal gangue as the primary material and three other mineral powders as auxiliary materials, including K-feldspar, CaCO3 and fly ash. A systematic analysis was conducted to explore the optimum raw material addition ratio and optimum sintering temperature; then, the intrinsic structure of thermal insulation bricks and their sintering formation mechanisms were revealed. The results showed that the optimal ratios of coal gangue, K-feldspar, CaCO3 and fly ash were 65 wt%, 15 wt%, 10 wt% and 10 wt%, respectively; the compressive strength of the thermal insulation brick produced under this ratio was 22.5 MPa; thermal conductivity was 0.39 W m-1 k-1. During sintering processes, mineral powders sufficiently fused to form a skeleton, and the CO2 derived from CaCO3 formed pores. The optimum sintering temperature was 1150 °C, because at this temperature, K-feldspar had the best effect in promoting the conversion of CaCO3 to Ca-feldspar. The high level of the relative crystallinity of Ca-feldspar (about 76.0%) helped raise the Si-O network's polymerization degree (NBO/T = 1.24), finally raising the compressive strength of thermal insulation bricks. The innovative method of using coal gangue to make thermal insulation bricks not only solved the environmental pollution caused by coal gangue but also provided excellent construction materials with high practical application value.

A Study on an Easy-Plane FeSi3.5 Composite with High Permeability and Ultra-Low Loss at the MHz Frequency Band.

An easy-plane FeSi3.5 composite with excellent magnetic properties and loss properties at MHz were proposed. The easy-plane FeSi3.5 composite has ultra-low loss at 10 MHz and 4 mT, about 372.88 kW/m3. In order to explore the reason that the Pcv of easy-plane FeSi3.5 composite is ultra-low, a none easy-plane FeSi3.5 composite, without easy-plane processing as a control group, measured the microstructure, and the magnetic and loss properties. We first found that the real reason why magnetic materials do not work properly at MHz due to overheat is dramatical increase of the excess loss and the easy-plane composite can greatly re-duce the excess loss by loss measurement and separation. The total loss of none easy-plane FeSi3.5 composite is much higher than that of easy-plane FeSi3.5 composite, where the excess loss is a major part in the total loss and even over 80% in the none easy-plane FeSi3.5 composite. The easy-plane FeSi3.5 composite can greatly reduce the total loss compared to the none easy-plane FeSi3.5 composite, from 2785.8 kW/m3 to 500.42 kW/m3 (3 MHz, 8 mT), with the main reduction being the excess loss, from 2435.2 kW/m3 to 204.93 kW/m3 (3 MHz, 8 mT), reduced by 91.58%. Furthermore, the easy-plane FeSi3.5 composite also has excellent magnetic properties, high permeability and ferromagnetic resonance frequencies. This makes the easy-plane FeSi3.5 composite become an excellent soft magnetic composite and it is possible for magnetic devices to operate properly at higher frequencies, especially at the MHz band and above.

Case Report: Advanced pulmonary sarcomatoid carcinoma with adrenal gland metastasis after sintilimab combined with anlotinib treatment.

Background: Pulmonary sarcomatoid carcinoma (PSC) is a rare subtype of non-small-cell lung cancer (NSCLC), which is resistant to conventional chemotherapy and radiotherapy with a poor prognosis. The MET inhibitor may be effective for the patients with MET exon 14 skipping mutation. This mutation was not detected in this patient. However, the PD-L1 TPS 60%, KRAS and TP53 mutations were detected in this patient could benefited from immunotherapy. The anlotinib is a novel multitarget antiangiogenic drug that could be effective for advanced non-small-cell lung cancer and some sarcoma patients. We report a patient with advanced pulmonary sarcomatoid carcinoma successfully treated with immunotherapy combined with antiangiogenic drugs. Case summary: A 75-year-old male was admitted to the hospital in July 2020 because of productive cough for more than three months. The patient was diagnosed with advanced pulmonary sarcomatoid carcinoma with adrenal gland metastasis (cT4N3M1b, stage IVA) was treated in our hospital. Genetic testing revealed KRAS P.L19F mutation (abundance 19.12%) and NFEE2L2 P.E82G mutation (abundance 14.84%); TP53 P.S183 mutation (abundance 26.97%), TMB(Tumor Mutational Burden) 30.91 muts/Mb, MSS, and PD-L1 (Daco 22C3) TPS 60% were also detected. We administrated sintilimab combined with anlotinib treatment, a PD-1 inhibitor with antiangiogenic drug. The patient achieved a favorable outcome with tolerable adverse effects. Conclusion: Sintilimab combined with anlotinib treatment may lead to a favorable outcome for patients with advanced pulmonary sarcomatoid carcinoma.

New insights on precise regulation of pollutant distribution inside a street canyon by different vegetation planting patterns.

Mixed-vegetation planting patterns are commonly seen in urban areas for specific reasons like aesthetic, cooling, and particle deposition effects of the vegetation. However, they may have a negative impact on human health by worsening the air quality inside the street canyon due to the decreased air exchange rate. From the view of precise control of pollutant concentration in the sensitive areas of people's concern in the existed street canyons, thirty-four cases with different vegetation planting patterns and pressure loss coefficients (λ) are studied numerically to investigate the effects of vegetation on airflow and pollutant dispersion inside the canyon. The cases of treeless and 2 rows of tree planting patterns in wind-tunnel measurements were selected for the model validation. The results demonstrate that compared to the treeless case, the greenbelts can greatly change the airflow features and reduce the pollutant concentration at the leeward side, while the only-tree planting patterns have little impact on the flow and deteriorate dispersion within the street canyon. Moreover, rows of greenbelts planted under the corresponding trees can reduce the average pollutant concentrations on the leeward wall and the footpath of the street canyon by up to 22.6% and 33.2%, respectively. Besides, the pattern of 1 row of trees with 1 row of greenbelts planted in the street canyon center should be suggested as the optimal mixed vegetation configuration in this study. That is because compared to the treeless case the pollutant concentration on leeward wall, windward wall, leeward footpath, and windward footpath can be reduced by 14.2%, 10.0%, 24.6%, and 37%, respectively. It is helpful to the city planners to consider whether the disadvantages of planting vegetation inside the street canyon would overwhelm the advantages.

Evaluation on ventilation and traffic pollutant dispersion in asymmetric street canyons with void decks.

With continuous global warming, growing urban population density, and increasing compactness of urban buildings, the "void deck" street canyon design has become increasingly popular in city planning, especially for urban streets located in tropical areas. Nevertheless, research on traffic pollutant dispersion in street canyons with void decks (VDs) is still at its early stage. This study quantitatively evaluates the effects of void deck height and location on the canyon ventilation and pollutant dispersion in asymmetric street canyons with void decks, and the pollutant exposure risk level for pedestrians and street dwellers. Void decks introduce more fresh air, thereby greatly improving the ventilation properties of the asymmetric canyon. The air exchange rate (ACH: 147.9%, 270.9%) and net escape velocity (NEV*: 416.7%, 915.8%) of the step-up and step-down canyons with VDs (3 m high at full scale) at both buildings are higher than those of regular asymmetric canyons. Moreover, the mean dimensionless pollutant concentration (K) on the building wall and pedestrian respiration plane in which VDs are located stands at a low level, because pollutants are removed by the airflow entering or exiting through the void decks. Increased VD height (4.5 m at full scale) enhances the strength of airflow flowing into and out of the canyon, significantly increasing ACH (177.3%, 380.9%) and NEV* (595.2%, 1268.4%) and decreasing the mean K on both pedestrian respiration planes and canyon walls. In particular, the K values on both pedestrian respiration planes and both walls are almost zero for the canyons with VDs at both buildings. Therefore, among the three VD locations, both VDs provide the best living environment for pedestrians and near-road residents. These findings can help to design urban street canyons for mitigating traffic pollution risk and improving ventilation in tropical cities.

Enhancement of coal gangue performance by surface micro-crystalline glaze derived from mineral powder.

Coal gangue is a waste derived from coal mining, and its unreasonable disposal usually causes serious land occupation and environmental pollution. Using coal gangue as a substitute for natural aggregate is an effective recycling approach, however, the high water absorption and high crushing rate of coal gangue seriously weaken its performance. This study proposed a novel strategy to decrease the water absorption and crushing rate of coal gangue by co-calcining with mineral powders, including K-feldspar, wollastonite, blast furnace slag and fly ash, meanwhile clarified the improvement mechanisms. Results showed that after calcining with mineral powders, the crushing rate of coal gangue decreased from 16.8 % to 16.1-13.2 %, and water absorption decreased from 5.29 % to 2.74-3.90 %, among which the coal gangue treated by K-feldspar and blast furnace slag had the lowest water absorption (2.74 %), reducing by 48.2 % compared to raw coal gangue. Underlying mechanisms were that during calcination, mineral powders generated micro-crystalline glaze on gangue surface, which improved the pore size distribution of coal gangue and strengthened its hardness. Specifically, as for pores with 1-1000 nm diameter, the pore volume percentage decreased from 88.5 % to 43.2-71.3 %. Vickers hardness of coal gangue increased from 0.29 GPa to 6.37-6.79 GPa, and the fracture toughness increased significantly to 41.9-67.6 MPa m1/2. Under K-feldspar and blast furnace slag treatment, the approximate thickness of micro-crystalline glaze was about 32 µm. The main component of micro-crystalline glaze was silicate lattice derived from SiO2 and Al2O3, and abundant Fe2O3 and Fe3O4 crystalline were sealed in the glaze. This study provides an innovative approach to strengthen the performance of coal gangue, which is important to expand the resource utilization of coal gangue and control the environmental pollution.

Influence of wind direction on the ventilation and pollutant dispersion in different 3D street canyon configurations: numerical simulation and wind-tunnel experiment.

Configuration of street canyon and the wind environment have a great influence on the self-ventilation capacity of the canyon, but the couple-effect of these two factors could not be considered in the previous study. The purpose of this study is to clarify the couple effect of street canyon configuration and wind environment on the ventilation and pollutant dispersion inside the street canyon. For this purpose, five wind directions of α = 90°, 60°, 45°, 30°, and 0° (α is the angle between the approaching wind and street canyon) and three canyon configurations (flat, step-up, and step-down canyons) were considered with numerical simulation and wind-tunnel experiment. Meanwhile, ACH (air exchange rate) and NEV (net escape velocity) were used to evaluate the ventilation capacity of the canyon. The results reveal that the wind direction has a vital influence on the ventilation in the different canyon configurations. Under the parallel wind direction (α = 0°), the airflow and ventilation capacity inside the three canyons are similar. Relative difference of ACH, named as RDA ((ACHasymmetric-ACHsymmetric)/ACHsymmetric [Formula: see text] 100%), is 1.82%. However, under the oblique (α = 30°, 45°, and 60°) and perpendicular wind direction (α = 90°), the airflow of the step-down canyon is very different from the step-up and flat canyons. In step-down canyons, reverse flow occurs under the oblique and perpendicular wind direction, and the strength of the reverse flow increases as α increases. Due to this reverse flow, the ventilation capacity of the step-down canyon is lower than that of the step-up and flat canyons. As for the ventilation capacity in the pedestrian respiration domain, the ventilation capacity of the leeward pedestrian domain (leeward NEV) is higher in the step-down canyon than in the step-up canyon and the flat canyon (when α = 90°, leeward NEV of step-down canyon is 2.47 times the flat canyon). Conversely, the ventilation capacity of the windward pedestrian domain is lower in step-down canyons than in step-up or flat canyon (when α = 90°, windward NEV of step-down canyon is 0.1 times that of step-up canyon). The aforementioned findings are helpful to understand the effects of canyon configurations together with wind directions on the airflow as well as pollutant concentration inside the canyon. Although further researches are still required to provide practical guidelines, this study present effective methodologies to quantify the influences of street configurations and wind directions on street canyon ventilation for urban design purpose.

Effects of Radiant Floor Heating Integrated with Natural Ventilation on Flow and Dispersion in a Newly Decorated Residence.

To date, few studies have been conducted on the characteristics of flow and dispersion caused by indoor radiant floor heating integrated with natural ventilation. In this study, we employed reduced-scale numerical models validated by wind-tunnel experiments to investigate the influence of radiant floor heating integrated with natural ventilation on airflow, heat transfer, and pollutant dispersion within an isolated building. The Richardson number (Ri) was specified to characterize the interaction between the inflow inertia force and the buoyancy force caused by radiant floor heating. Several Ri cases from 0 to 26.65, coupled with cross- or single-sided ventilation, were considered. Model validation showed that the numerical model coupled with the RNG k-ε model was able to better predict the indoor buoyant flow and pollutant dispersion. The results showed that the similarity criterion of Ri equality should be first satisfied in order to study indoor mixed convection using the reduced-scale model, followed by Re-independence. For cross-ventilation, when Ri < 5.31, the incoming flow inertia force mainly dominates the indoor flow structure so that the ACH, indoor temperature, and pollutant distributions remain almost constant. When Ri > 5.31, the thermal buoyancy force becomes increasingly important, causing significant changes in indoor flow structures. However, for single-sided ventilation, when Ri > 5.31 and continues to increase, the buoyancy force mainly dominates the indoor flow structure, causing a significant increase in ACH, thus reducing the indoor average temperature and pollutant accumulation.

Chlorine-Coordinated Pd Single Atom Enhanced the Chlorine Resistance for Volatile Organic Compound Degradation: Mechanism Study.

The development of catalysts with high chlorine resistance for volatile organic compound (VOC) degradation is of great significance to achieve air purification. Herein, Pd@ZrO2 catalysts with monodispersed Pd atoms coordinated with Cl were prepared using an in situ grown Zr-based metal-organic framework (MOF) as the sacrifice templates to enhance the chlorine resistance for VOC elimination. The residual Cl species from the Zr-MOF coordinated with Pd, forming Pd1-Cl species during the pyrolysis. Meanwhile, abundant oxygen vacancies (VO) were generated, which enhanced the adsorption and activation of gaseous oxygen molecules, accelerating the degradation of VOCs. In addition, the Pd@ZrO2 catalysts exhibited satisfactory water resistance, long-term stability, and great resistance to CO and dichloromethane (DCM) for VOC elimination. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results elucidated that the generation of Pd1-Cl species in Pd@ZrO2 suppressed the absorption of DCM, releasing more active sites for toluene and its intermediate adsorption. Simultaneously, the monodispersed Pd atoms and VO improved the reactivity of gaseous oxygen molecule adsorption and dissociation, boosting the deep decomposition of toluene and its intermediates. This work may provide a new strategy for rationally designing high-chlorine resistance catalysts for VOC elimination to improve the atmospheric environment.

Effects of void deck on the airflow and pollutant dispersion in 3D street canyons.

In general, urban canyons are the areas most clearly affected by traffic pollutants since the ability of the canyon to self-ventilate is inhibited due to blockage of buildings or other urban structures. However, previous studies have aimed to improve the pedestrian-level wind speed with void deck in single buildings or short canyons. This study investigated the effects of void deck height and location, and the building height on the airflow field and the traffic pollutant diffusion in a long canyon with L/H = 10, validated by wind-tunnel experiment data. The results show that the void decks have a significant effect on the airflow and pollutant distribution inside the canyon. Air exchange rates (ACH) of the canyons with the void deck are much larger than that of regular canyons, and the perturbation changes of turbulence (ACH') decrease. For the windward void deck, purging flow rate (PFR) and normalized net escape velocity (NEV*) increase by 6.4 times compared to the regular canyon, and for the leeward void deck, increase by 13 times. In particular, when the void decks are at both buildings, they are increased by 38.3 times. Also, for the canyons with the void deck, traffic pollutants are removed out of the canyon by the strong airflow through the void deck. Therefore, unlike the regular canyons, as the void deck and the building height increases, the strength of the airflow through the void deck becomes stronger, and as a result, the mean pollutant concentration is significantly reduced at both walls and the pedestrian respiration level. The mean pollutant concentration on the wall of the building with the void deck and on the pedestrian respiration plane close to it is near zero. These findings can help ease traffic pollution inside the street canyons composed of high-rise buildings, especially in tropical cities.

Emission characteristics and impact factors of air pollutants from municipal solid waste incineration in Shanghai, China.

The emission of air pollutants from the municipal solid waste (MSW) incineration is one of the major concerns in air pollution. The up-to-date emission situation for Chinese MSW incineration is largely unknown. The emission factors (EFs) are the key parameters to estimate the emissions from MSW incineration. The localized EFs from MSW incineration in Shanghai, China were established using continuous emission monitoring system data from 2017 to 2019. Our results showed that the EFs were 9.80 g t-1 of PM, 46.62 g t-1 of SO2, 812.68 g t-1 of NOx, 25.84 g t-1 of CO, and 17.49 g t-1 of HCl for the period 2017-2019, nearly 1.7-24.2 times lower than those in 2010, implying that the current EFs should be updated to avoid overestimation of MSW emissions in China. Compared with 2010, the emissions of PM, SO2, CO, and HCl in 2019 were significantly reduced by 84%, 69%, 47%, and 72%, respectively, except for NOx with a 106% increase, although the corresponding MSW incineration amount increased by 356%. The current levels of air pollutants from MSW incineration have already met the current national emission standard as well as the stricter standard of the European Union (98.87%-99.91%). Our findings suggest that China should update the current standards of MSW incineration, which can be a benefit for the prevention and control of MSW incineration in the future. It is still challenging to control NOx emissions from MSW incineration for Shanghai and even greater China.

Comments on using of "pseudo-first-order kinetic model" [Sci. Total Environ. 750 (2021) 142370, 750 (2021) 141498, 761 (2021) 143229].

A mistake of applying pseudo-first-order (PFO) kinetic model in the three papers has been pointed out. Also a correct PFO kinetic equation is given. In addition, a suggestion is made for avoiding using erroneous PFO kinetic equations in adsorption systems.

Numerical studies on issues of Re-independence for indoor airflow and pollutant dispersion within an isolated building.

This study conducted the numerical models validated by wind-tunnel experiments to investigate the issues of Re-independence of indoor airflow and pollutant dispersion within an isolated building. The window Reynolds number (Re w ) was specified to characterize the indoor flow and dispersion. The indicators of RRC (ratio of relative change) or DR (K_DR) (difference ratio of dimensionless concentration) ≤ 5% were applied to quantitatively determine the critical Re w for indoor flow and turbulent diffusion. The results show that the critical Re (Re crit) value is position-dependent, and Re crit at the most unfavorable position should be suggested as the optimal value within the whole areas of interest. Thus Re H,crit = 27,000 is recommended for the outdoor flows; while Re w,crit = 15,000 is determined for the indoor flows due to the lower part below the window showing the most unfavorable. The suggested Re w,crit (=15,000) for indoor airflow and cross ventilation is independence of the window size. Moreover, taking K_DR ≤ 5% as the indicator, the suggested Re w,crit for ensuring indoor pollutant diffusion enter the Re-independence regime should also be 15,000, indicating that indoor passive diffusion is completely determined by the flow structures. The contours of dimensionless velocity (U/U 0) and concentration (K) against the increasing Re w further confirmed this critical value. This study further reveals the Re-independence issues for indoor flow and dispersion to ensure the reliability of the data obtained by reduced-scale numerical or wind-tunnel models.

[Distribution, Source, and Ecological Risk Evaluation of the PAHs and PCBs in the Sediments from Sanya River].

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), two typical persistent organic pollutants, are the research focus due to their mutagenesis, carcinogenesis, teratogenesis, and bioaccumulation. The content distribution and residual characteristics of PAHs and PCBs were investigated in the sediments from the Sanya River. Source apportionment was further explored based on the analysis of the spatial distribution, and the ecological risk evaluation was carried out with the sediment quality criteria and standards. The results indicate that the content of ΣPAHs and ΣPCBs in the sediment range from 265.00 µg·kg-1 to 6735.00 µg·kg-1 and 1.75 µg·kg-1 to 92.75 µg·kg-1, with relatively high contents in the east and west river upstream, respectively, which had a strong correlation with the industrial structure and river movement of the study area. The composition and source apportionment demonstrate that PAHs originated mostly from the combustion of petroleum with low PAHs, and haxa-CB and hepta-CB are the predominant PCBs congeners, primarily resulting from the migration of PCBs in the capacitor. The ecological risk evaluation demonstrates that the biotoxic effect of the PAHs is not obvious, with a low ecological risk. However, several PAHs monomers exceeded the standard significantly in some sampling sites, which should be of concern due to its serious threat of exposure to organisms. The probability of a biotoxic effect of PCBs is 10%-50%, which occasionally produces a negative ecological effect.

New insights into the underlying influence of bentonite on Pb immobilization by undissolvable and dissolvable fractions of biochar.

Biochar as a green amendment has been used to immobilize heavy metals in contaminated soil. Apart from the importance of the amendment itself, the interaction with soil components like clay minerals might also influence the immobilization behavior of biochar. Here, we examined the impact of a typical soil mineral, bentonite, on the immobilization of Pb by barley grass-derived biochar, and elucidated the underlying mechanisms by dividing biochar into dissolvable and undissolvable fractions. Results showed that biochar and bentonite could immobilize Pb through mechanism of electrostatic sorption, complexation, and precipitation. Compared to sole undissolvable biochar, coexistence of bentonite rapidly raised pH of the mixture over 7.0, leading the free Pb2+ transformed into more stable Pb2CO3(OH)2 (Ksp = 1.3 × 10-18) instead of PbCO3 (Ksp = 1.5 × 10-13), finally increased Pb2+ removal rate by 1.47 times. As for the dissolvable biochar, the generation of dissolvable biochar-bentonite-Pb2+ ternary complex raised the Pb2+ removal rate by 59.6% with the presence of bentonite. Small angel XRD analysis showed that the free Pb2+ and dissolvable biochar-associated Pb2+ could enter the interlayer space of bentonite and thus expanded the d-spacing from 1.28 nm to 1.36-1.50 nm, which might favor the formation of ternary complex. Findings of this study not only provided a new insight into the immobilization of heavy metals by biochar in soil, but also emphasized the importance of interaction between biochar and soil minerals.

Stabilization of dissolvable biochar by soil minerals: Release reduction and organo-mineral complexes formation.

Biochar has two existing forms in the moist soil environment, free dissolvable biochar (particle size < 0.45 µm) and undissolvable particles (particle size > 0.45 µm). The release and decomposition of dissolvable biochar from bulk biochar particles is a primary C loss pathway in biochar-amended soils, which would be reduced by their interactions with soil minerals. Most previous studies focused on the effect of feedstock types and pyrolysis conditions on dissolvable biochar stability, while few studies researched the interaction between dissolvable biochar and soil components, for instance the soil minerals, and its effect on the stability of dissolvable biochar. In this study, bentonite and goethite were selected as model soil minerals because of their differences in structure and surface types: negatively charged 2:1 type phyllosilicate (bentonite) and positively charged crystalline mineral (goethite). Dry-wet cycling was conducted to determine the effect of these two minerals on the release of dissolvable biochar from walnut shell-derived biochar particles. The stability of dissolvable biochar was measured by chemical oxidation and biodegradation. Both soil minerals reduced the release of dissolvable biochar by over 34% with the presence of Ca2+. Mechanisms of "Ca2+ bridging", "ligand exchange" and "van der Waals attraction" contributed to the formation of dissolvable biochar-bentonite complexes, and Ca2+ promoted dissolvable biochar inserting into bentonite interlayer space, expanding d-spacing from 1.25 nm to 1.55 nm. However, "Ca2+ bridging" barely formed on goethite because of charge repulsion, indicating that the dissolvable biochar was bound with goethite mainly by "van der Waals attraction" and "ligand exchange". Due to organo-mineral complexes formation, the chemical oxidation extent of dissolvable biochar was reduced by 22.8-36.5%, and the biodegradation extent was reduced by 72.7-85.0%, since the soil minerals are more effective to prevent the dissolvable biochar from being biodegraded. This study proved soil minerals and Ca2+ were beneficial for enhancing biochar stability, these observations assisted in assessing the biochar ability for long-term carbon sequestration.