Spatial distribution and risk assessment of heavy metal pollution from enterprises in China.

Heavy metal pollution (HMP) directly affects the safety of agricultural products, thereby impacting human health. Industrial emissions, as the main source of soil HMP in China, require in-depth research on their pollution risks. Based on national heavy metal (HM) enterprise data, this paper analyzes the spatial distribution characteristics of key enterprises involved in the HMP across the country. It constructs the risk assessment index system of enterprise HMP based on the "source-pathway-receptor" (SPR) process of the HMP, evaluates and partitions the risk of the HMP from enterprises nationwide. The results show that: (1) Enterprises and pollutant discharge outlets are mainly distributed in the eastern and southeastern coastal regions. Jiangxi, Yunnan, Guangdong, and Hunan Province are the main distribution regions of smelting enterprises, with the most types of HM pollutants. The hazard of pollution sources shows a spatial distribution pattern of higher risk in the southwest and north, and lower risk in the central region. Counties with high-risk pollution sources are mainly distributed in Yunnan, Hunan, Guangdong, Inner Mongolia, and Jiangxi Province. (2) The hazard of pollutant transmission pathways shows a spatial distribution pattern of higher risk in the southeast and lower risk in the central region. About 31.5 % of counties are at extremely high risk, mainly distributed in the southeastern coastal regions of Guangdong, Jiangsu, Zhejiang, Jiangxi, Shandong, and Fujian Province. (3) The vulnerability of the receptors shows significant clustering characteristics in the northeast and central regions. About 3.3 % of counties have a receptor vulnerability level of "extremely high," mainly distributed in Inner Mongolia, Jilin, Heilongjiang, Liaoning Province in the northeast, as well as Hubei and Jiangsu Province. (4) About 1.55 % of counties nationwide have a comprehensive risk level of the HMP classified as "extremely high," mainly distributed in Guangdong Province and Inner Mongolia. Additionally, some counties in Yunnan, Hunan, Jiangsu, Jiangxi, and Zhejiang Province have a risk of exceeding pollution standards, requiring further preventive measures to reduce pollution risks in the future. This paper can provide a scientific basis for the prevention and control (P&C) of the HMP in China.

Unravelling structure evolution of dissolved organic matter during oxidation by persulfate: Insights from aromaticity and fluorescence analysis.

Persulfate advanced oxidation technology is widely utilized for remediating organic-contaminated groundwater. Post-remediation by persulfate oxidation, the aromaticity of dissolved organic matter (DOM) in groundwater is significantly reduced. Nevertheless, the evolution trends of aromaticity and related structural changes in DOM remained unclear. Here, we selected eight types of DOM to analyze the variation in aromaticity, molecular weight, and fluorescence characteristics during oxidation by persulfate using optical spectroscopy and parallel faction analysis combined with two-dimensional correlation spectroscopy analysis (2D PARAFAC COS). The results showed diverse trends in the changes of aromaticity and maximum fluorescence intensity (Fmax) among different types of DOM as the reaction time increases. Four types of DOM (humic acid 1S104H, fulvic acid, and natural organic matters) exhibited an initially noteworthy increase in aromaticity followed by a decrease, while others demonstrated a continuous decreasing trend (14.3%-69.4%). The overall decreasing magnitude of DOM aromaticity follows the order of natural organic matters ≈ commercial humic acid > fulvic acid > extracted humic acid. The Fmax of humic acid increased, exception of commercial humic acid. The Fmax of fulvic acid initially decreased and then increased, while that of natural organic matters exhibited a decreasing trend (86.4%). The fulvic acid-like substance is the main controlling factor for the aromaticity and molecular weight of DOM during persulfate oxidation process. The oxidation sequence of fluorophores in DOM is as follows: fulvic-like substance, microbial-derived humic-like substance, humic-like substance, and aquatic humic-like substance. The fulvic-like and microbial-derived humic-like substances at longer excitation wavelengths were more sensitive to the response of persulfate oxidation than that of shorter excitation wavelengths. This result reveals the structure evolution of DOM during persulfate oxidation process and provides further support for predicting its environmental behavior.

Bio-accumulation and health risk assessments of per- and polyfluoroalkyl substances in wheat grains.

Per- and polyfluoroalkyl substances (PFASs) have been widely detected in various food, which has attracted worldwide concern. However, the factors influencing the transfer and bio-accumulation of PFASs from soils to wheat in normal farmland, is still ambiguous. We investigated the PFASs accumulation in agricultural soils and grains from 10 cites, China, and evaluated the health risks of PFASs via wheat consumption. Our results show that ∑PFASs in soils range from 0.34 µg/kg to 1.59 µg/kg with PFOA and PFOS dominating, whilst ∑PFASs in wheats range from 2.74 to 6.01 µg/kg with PFOA, PFBA and PFHxS dominating. The lower pH conditions and high total organic carbon (TOC) could result in the higher accumulation of PFASs in soils and subsequently in wheat grains, whilst the bioaccumulation factors of PFASs increase with increasing pH conditions but not with TOC. The estimated daily intake (EDI) values of PFBA, PFOA, and PFHxS are relatively high, but data supports that ingesting wheat grains does not result in any potential risk to the human beings. Our studies provided more information about PFASs accumulation in wheat grains, and help us understand the current potential risks of PFASs in food.

Can arsenic bioavailability be predicted in soils using in vitro gastro-intestinal simulation?

Many gastrointestinal simulation methods have been used to predict bioavailability, but the suitability of different methods for the same metal(loid)s varies widely, which inevitably affects the accuracy of human health risk assessment. Arsenic is a common and important contaminant in many contaminated land situations. It can be readily absorbed and has teratogenic and mutagenic toxicity. Therefore, in this study, four the most commonly used in vitro simulation methods (the Physiologically Based Extraction Test (PBET), In Vitro Gastrointestinal Method (IVG), Soluble Bioavailability Research Consortium (SBRC), the Unified BARGE Method (UBM)) were tested against an in vivo animal live model, to evaluate their effectiveness for the prediction of soil As bioavailability in 10 industrially contaminated soils. The soil As relative bioavailability (RBA) varied between 15% and 68% in the different soils. As bioaccessibility differed between the 4 gastro-intestinal simulation methods. Gastric phase of UBM (UBMG) predicted As relative bioavailability the best of the 4 assays (R2 = 0.81). This study provides theoretical and technical support to refine human health risk assessment of As in soils from urban industrial legacy contaminated sites.

Effects of freeze-thaw action on in vivo and in vitro bioavailability of arsenic in soils from derelict industrial sites.

Arsenic is a metalloid with carcinogenic properties and has been classified as a Category I carcinogen by the International Agency for Research on Cancer (IARC). Freeze-thaw processes affect the migration and transformation of soil heavy metals, as well as adsorption/desorption and redox reactions. However, there is limited research directly addressing the impact of freeze-thaw processes on the bioavailability of soil heavy metals. In this study, we focused on As and selected As-contaminated soil samples from three types of legacy sites in heavy industrial areas. Under controlled freeze-thaw experimental conditions, we utilized both in vivo and in vitro bioavailability measurement methods to investigate whether and how freeze-thaw processes affect the bioavailability of soil As. The results of this study showed that freeze-thaw processes reduced soil pH (P < 0.05), CEC, SOM, and particle size, with decreases of 0.33, 1.2 cmol/kg, 5.2 g/kg, and 54 µm, respectively. It also increased weight specific surface area (BET) (P < 0.05), with an increase of 300 m2/kg. Freeze-thaw processes increased the proportions of exchangeable (P < 0.05), carbonate-bound, and iron-manganese oxide-bound As (P < 0.05), but reduced the proportions of organic-bound and residual As (P < 0.05). Freeze-thaw processes significantly increased the relative bioavailability and bioaccessibility of As, with increases of 32 ± 9.6% and 13 ± 0.23%, respectively. Soil pH, SOM, BET and electronic conductivity (EC) were identified as factors which could contribute to the increased bioavailability of As due to freeze-thaw processes. These results provide new insights and evidence for refining the assessment of human health risks associated with heavy metal contamination in polluted soils.

Structural and mineralogical variation upon reoxidation of reduced Fe-bearing clay minerals during thermal activation.

The hydroxyl radicals (OH) produced from Fe(II) oxidation upon reoxidation of reduced Fe-bearing clay minerals (RFC) have received increased attention and thermal activation was used to enhance Fe(II) oxidation to improve OH production. However, changes in mineral morphology and structure during thermally-activated RFC reoxidation are not yet clear. Herein, the Fe(II) oxidation extent was measured by chemical analysis during the reoxidation of model RFC (reduced nontronite (rNAu-2) at elevated temperatures. Mineralogical variation of rNAu-2 particles was observed by scanning electron microscopy (SEM), Mössbauer spectra, and X-ray photoelectron spectroscopy (XPS). The structural Fe(II) oxidation in rNAu-2 was accelerated with increasing temperature, accompanied by the transformation of structural entities and the dissolution of Fe and Si, while the overall structure of rNAu-2 minerals was relatively intact. The surface microstructure of particles showed the dissolved holes, net-shape flocs, and even large pore channels after Fe(II) oxidation by thermal activation. Moreover, the rearrangement of structural Fe(II) entities, the regeneration of edge Fe(II), and the electron transport from the interior to the edge were enhanced during rNAu-2 reoxidation by thermal activation. The increasing electron transfer at elevated temperatures could possibly be owing to the increasing number of reactive sites by increasing the internal disorder of rNAu-2. This work provides novel insights into the structural and mineralogical changes in promoting electron transfer upon RFC reoxidation.

A numerical simulation of thermally-enhanced soil vapor extraction with a validation of an actual contaminated site.

Thermally-enhanced soil vapor extraction (T-SVE) remediation technology is widely used in organic-contaminated sites due to its high efficiency, short remediation period and controllable secondary contamination. However, the remediation efficiency is affected by the complex site factors, which leads to the uncertainty of the remediation process and energy waste. Thus, it is necessary to optimize T-SVE systems to accurately remediate the sites. In this work, a pilot site of reagent factory in Tianjin was taken as the research object to validate the model, and the T-SVE process parameters of a VOCs-contaminated sites were predicted by this simulation method. The simulation results showed that the Nash efficiency coefficient E of the measured and simulated temperature rise data in the study area was 0.885, and the linear correlation coefficient R of the measured and simulated concentrations of cis-1,2-dichloroethylene after remediation was 0.877, indicating that this simulation method is highly reliable. Based on this numerical simulation method, some parameters of the T-SVE process at the VOCs-contaminated site of an insulation plant in Harbin were simulated and optimized. Included a heating well spacing of 3.0 m, extraction pressure of 40 Kpa, extraction well influence radius of 4.35 m, extraction flow rate of 2.97 × 10-4 m3/s, and a theoretical number of 25 extraction wells (adjusted to 29 wells in practice), and the corresponding extraction well layout has been designed. The results can provide a technical reference for the future application of T-SVE in the remediation of organic-contaminated sites.

Insights into the mechanism of persulfate activation with biochar composite loaded with Fe for 2,4-dinitrotoluene degradation.

Iron in biochar composite loaded with Fe (Fex@biochar) is crucial for persulfate activation. However, the iron dosages-driven mechanism linked to the speciation, electrochemical property, and persulfate activation with Fex@biochar remains ambiguous. We synthesized and characterized a series of Fex@biochar and evaluated its catalytic performance in 2,4-dinitrotoluene removal experiments. With increasing FeCl3 dosage, iron speciation in Fex@biochar changed from γ-Fe2O3 to Fe3O4, and the variation in functional groups was as follows: Fe-O, aliphatic C-O-H, O-H, aliphatic C-H, aromatic CC or CO, and C-N. The electron accepting capacity of Fex@biochar increased as the FeCl3 dosage increased from 10 to 100 mM but decreased at 300 and 500 mM FeCl3. 2,4-dinitrotoluene removal first increased and subsequently decreased, reaching 100% in the persulfate/Fe100@biochar system. The Fe100@biochar also showed good stability and reusability for PS activation, verified by five test cycles. The mechanism analysis indicated that the iron dosage altered the Fe (Ⅲ) content and electron accepting capacity of Fex@biochar during pyrolysis, further controlling persulfate activation and 2,4-dinitrotoluene removal. These results support the preparation of eco-friendly Fex@biochar catalysts.

Spatial distribution, contamination characteristics and ecological-health risk assessment of toxic heavy metals in soils near a smelting area.

Soil heavy metals (HMs) contamination stemming from smelting and mining activities is becoming a global concern due to its devastating impacts on the environment and human health. In this study, 128 soil samples were investigated to assess the spatial distribution, contamination characteristics, ecological and human health risk of HMs in soils near a smelting area by using BP artificial neural network (BP-ANN) and Monte Carlo simulation. The results showed that the concentrations of all five HMs in the soil greatly exceeded the background value of study area with a basic trend: Pb > As > Cr > Cd > Hg, indicating a high pollution level. Arsenic and lead were the major pollutants in the study area with an exceedance rate of 78.95% and 28.95%, respectively. The toxic fume and dust emitted during the smelting process were identified as the major sources of HMs pollution in soil, while Cd pollution was mainly caused by agricultural activities near the study area. The probabilistic risk assessment suggested that the average HQ values of five HMs for children and adults exceeded the acceptable threshold with a trend: As > Pb > Cr > Cd > Hg. The average CR values of As, Cr and Pb for all population were greatly larger than the acceptable threshold (CR ≥ 1), indicating a high cancer risk. However, the CR values of Cd for adults and children were within the acceptable threshold (CR < 1), implying no cancer risk. The results of the present study can provide some insight into the contamination characteristics, ecological and human health risk of HMs in contaminated soils by mining and smelting activities, which can help prevent and control soil pollution and environmental risk.

Risk Control Values and Remediation Goals for Benzo[a]pyrene in Contaminated Sites: Sectoral Characteristics, Temporal Trends, and Empirical Implications.

Benzo[a]pyrene (BaP) is a highly carcinogenic pollutant of global concern. There is a need for a comprehensive assessment of regulation decisions for BaP-contaminated site management. Herein, we present a quantitative evaluation of remediation decisions from 206 contaminated sites throughout China between 2011 and 2021 using the cumulative distribution function (CDF) and related statistical methodologies. Generally, remediation decisions seek to establish remediation goals (RGs) based on the risk control values (RCVs). Cumulative frequency distributions, followed non-normal S-curve, emerged multiple nonrandom clusters. These clusters are consistent with regulatory guidance values (RGVs), of national and local soil levels in China. Additionally, priority interventions for contaminated sites were determined by prioritizing RCVs and identifying differences across industrial sectors. Notably, we found that RCVs and RGs became more relaxed over time, effectively reducing conservation and unsustainable social and economic impacts. The joint probability curve was applied to model decision values, which afforded a generic empirically important RG of 0.57 mg/kg. Overall, these findings will help decision-makers and governments develop appropriate remediation strategies for BaP as a ubiquitous priority pollutant.

Insights into the impacts of chloride ions on the oxidation of 2,4-dinitrotoluene using ferrous activated persulfate: Removal efficiency, reaction mechanism, transformation pathway, and toxicity assessment.

Persulfate/Fe2+-based advanced oxidation processes are widely used to treat water contaminated with 2,4-dinitrotoluene (DNT). However, the oxidation of DNT by persulfate/Fe2+ in the presence of the chloride ion (Cl⁻) has not been addressed, and the transformation pathways and toxicities of the intermediate products remain unclear. In this study, the effect of different Cl⁻ concentrations on the oxidation of DNT was investigated by persulfate/Fe2+. After the addition of 1.0 mM Cl⁻ and 6 h of oxidation, the removal efficiency of DNT increased by 68.5%. Scavenging experiments and an electron spin resonance analysis suggested that Cl⁻ caused hydroxyl radicals to increase in content in the persulfate/Fe2+ system, thus promoting the removal of DNT. Eight intermediate products of DNT were accurately detected using high-resolution mass spectrometry, and the transformation pathways of DNT were proposed, including hydroxylation/oxidation, elimination of the nitro group, and chlorination process. The acute and chronic toxicities of the intermediate products decreased during the oxidation process, but chlorinated by-products posed a higher toxicological risk. This result is vital for the practical application and environmental safety evaluation of persulfate/Fe2+-based advanced oxidation.

A bibliometric analysis and assessment of priorities for heavy metal bioavailability research and risk management in contaminated land.

Risk assessment has been recognized as an important tool for evaluating heavy metal pollution and providing risk-based information for decision makers. In order to accurately assess the risk of heavy metals in contaminated soil to human health, it is necessary to conduct bioavailability studies on heavy metals in soil. Bioavailability of heavy metals in soils and the implications for risk assessment and land management/remediation has evolved over the decades and now has considerable practical and economic implications internationally. This article aims to explore its evolution by undertaking a bibliometric analysis of the research fields which have addressed heavy metal bioavailability in soils, with a focus on the risk assessment of contaminated land and human exposure to soil-borne metals. Bibliometric analysis techniques are applied to monitor and assess the changing research literature on the bioavailability of heavy metals in contaminated soils. Over 5000 articles were found for the period 1979-2020. The purpose was not to perform an exhaustive literature review, but to draw out trends and patterns in the literature, and to make observations on past and current priorities. Key words were extracted from the analysis and the roles of different countries in driving the research literature identified. Three phases in literature/subject development were identified. Between 1979 and 2000 (initial phase, 213 articles), studies used extraction procedures and solubility studies to investigate the roles of soil properties on metal form/speciation and focused on bioavailability to (crop) plants in agricultural soils. Between 2001 and 2010 (slow development phase, 1105 articles), attention switched to metals introduced in soil amendments and wastes, metal impacts on soil microbial processes, and incorporating bioavailability in risk assessment. More rigorous techniques were being used, such as the diffusive gradients in thin films technique, to better understand kinetic and metal speciation in soils and the quantitative relationship to bioavailability. By 2011-2020 (rapid development phase, 3137 articles), research was being conducted in many countries (site specific, often industrially contaminated and urban sites), with a focus shift to health risk assessment, remediation, and bioavailability to various ecological receptors (e.g., humans and animals), with the development of many methods of bioavailability (e.g., simulated gastrointestinal tract enzymolysis methods). Some priorities for research on soil heavy metal bioavailability are identified.

Insights into the degradation process of phenol during in-situ thermal desorption: The overlooked oxidation of hydroxyl radicals from oxygenation of reduced Fe-bearing clay minerals.

In-situ thermal desorption (ISTD) has attracted increasing attention owing to the efficient removal of organic contaminants from contaminated sites. However, it is poorly understood that whether and to what extent contamination degradation occurs upon oxygenation of reduced Fe-bearing clay minerals (RFC) in the subsurface during ISTD. In this study, we evaluated the mechanism of contaminant degradation upon oxygenation of reduced clay minerals during the ISTD. Reduced nontronite (rNAu-2) and montmorillonite (rSWy-3) were selected as RFC models. Results showed that thermal treatment during ISTD could significantly enhance phenol degradation, which increased from 25.8 % at 10 °C to 74.4 % at 70 °C in rNAu-2 and from 17.7 % at 10 °C to 49.8 % at 70 °C in rSWy-3. Correspondingly, the cumulative •OH at steady-state ([•OH]ss) increased by 3.7 and 1.5 times, respectively. The acceleration of Fe(II) oxidation with increasing temperature could be mainly responsible for [•OH]ss generation, which degrades phenol. Moreover, thermal treatment improved the fast oxidation of trioctahedral entities Fe(II)Fe(II)Fe(II) (TOF) and the slow oxidation of dioctahedral entities Fe(II)Fe(II) (DTF1), AlFe(II) (DAF1), and Fe(II)Fe(III) (DTF2). Our study suggests that the overlooked degradation progress of phenol by oxygenation of RFC during ISTD, and it could be favorable for contaminant degradation during remediation.

Does freeze-thaw action affect the extractability and bioavailability of Pb and As in contaminated soils?

As global warming intensifies, there will be increased uncertainty as to the environmental behavior and risks from heavy metals in industrial/legacy contaminated sites in permafrost regions. Bioavailability has been increasingly used for human health risk assessment of heavy metals in contaminated soils. Soil heavy metal bioavailability depends on soil physicochemical properties, and freeze-thaw affects soil physical, chemical and biological processes. However it is not clear whether freeze-thaw has an effect on the bioavailability of soil heavy metals. In this study, soils contaminated with Pb and As were collected from 10 industrial sites in northeast China. Extractability and bioavailability of soil Pb and As were determined by the Tessier sequential extraction method and four in vitro gastron-intestinal simulation methods under control and freeze-thaw treatments. The aims were: to compare the results of extraction and bioavailability from laboratory experiments which artificially simulate freeze-thaw conditions against control soils; to explore the correlation between bioavailability of Pb/As and soil properties. Freeze-thaw significantly decreased soil pH, and increased the soil weight surface area. Freeze-thaw decreased the percentage in the residual fraction, and increased the percentage of Pb and As in the exchangeable fraction, carbonate-bound fraction, Fe-Mn oxides-bound fraction and organic-bound fraction, relative to control soils. Freeze-thaw significantly increased Pb and As bioavailability compared to the controls. Pb and As released in the gastric phase of the four methods was significantly higher than that in the intestinal phase. Further analysis of correlations between Pb and As bioavailability and soil properties indicated that total concentrations of Al, Fe and Mn, particle size, and weight surface area significantly correlated to Pb and As bioavailability. Overall, this study demonstrated that freeze-thaw did influence the bioavailability of soil heavy metals. It suggests the freeze-thaw action should be comprehensively considered in the human risk assessment of soil pollutants in permafrost regions.

Speciation, in vitro bioaccessibility and health risk of antimony in soils near an old industrial area.

Antimony (Sb) contamination in soil has become a major environmental issue due to its adverse effects on ecosystems and human health. In this paper, 1255 soil samples were analyzed to investigate the distribution, speciation, in vitro oral bioaccessibility (8 soil samples) and human health risk of Sb in contaminated soils and its impacts on groundwater. The results showed that 4.38 % of the soil samples within the depth of 0-31 m exceeded the Risk Screening Values (RSV). Sb mainly existed in the residual fraction (38.05 % ∼ 94.22 %), Fe/Mn oxides (0.01 % ∼ 31.80 %) and the organic fraction (0.32 % ∼ 21.55 %) with poor mobility. The bioaccessibility of Sb was approximately <31 %. The total concentration of Sb (TSb) in soil was the dominant factor influencing the bioaccessible concentration of Sb (SbBio). Soil physiochemical properties such as Fe, Mn, and organic matter content (OM) also affected the magnitude of SbBio. Health risk assessment based on in vitro bioaccessibility suggested that the hazard quotient (HQ) of adults was within the acceptable level (HQ < 1) for industrial scenario, while the HQ of children and adults was greater than the acceptable level (HQ ≥ 1) for residential scenario, with a higher risk to children than adults. The results of the leaching experiment involving Dilution-Attenuation Factor (DAF) model suggested that the predicted maximum concentration of Sb in groundwater was 2.40 µg/L that is lower than the acceptable standard value (5 µg/L), implying that groundwater was not contaminated by Sb in soil. The findings of this study provide some insights into the speciation, in vitro bioaccessibility and health risk of toxic trace metals in contaminated soils and the potential environmental impacts.

Leaching Characteristics of Heavy Metals in the Baghouse Filter Dust from Direct-Fired Thermal Desorption of Contaminated Soil.

After thermal desorption, the total amount of heavy metals (HMs) is enriched in baghouse filter dust. To further understand the related environmental impact, the leaching characteristics under various conditions must be explored. Therefore, this study aimed to examine the leaching characteristics of seven HMs in the dust generated in the direct-fired thermal desorption process and to compare the differences in heavy metal leaching characteristics in the soil before and after thermal desorption. The leaching characteristics and bioaccessibility of seven HMs-arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn)-were analyzed in dust and in soil before and after thermal desorption. The activity of HMs in dust was strong. Therefore, environmental effects and effects on human health should be considered in the treatment of soil and dust after thermal desorption.

Fluoride-immobilized co-processing and resource utilization of aluminum-electrolyzed spent cathode carbon in brick-fired kiln.

Spent cathode carbon (SCC) is hazardous waste from the electrolytic aluminum industry due to its high levels of soluble fluoride, while brick-fired kiln provides the clay and heating conditions needed to immobilize fluoride. However, SCC reusing is still understudied, meanwhile co-processing and resource utilization of SCC in brick-fired kiln were still not reported in the literatures in addition to a Chinese patent of the authors. Here, the effects of firing temperatures, firing time, clay doses and calcium doses on the fluoride-immobilized performance of SCC co-processing were explored in a simulated brick-firing kiln, and their mechanisms were analyzed by SEM and XRD. The results indicated that clay-added co-processing in brick-fired kiln was a preferred choice without required additional additives or operations. The leached fluoride met Chinese standards by clay-added co-processing at ≥ 800 °C/ ≥ 40 g clay/ ≥ 120 min. Clay and calcium-added co-processing in brick-fired kiln was another alternative choice with higher fluoride-immobilization rates. The leached fluoride met Chinese standard (GB5085.3-2007) by clay and calcium-added co-processing at ≥ 500 °C/ ≥ 30 min/ ≥ 5 g clay/ ≥ 0.5 g CaCO3. SEM and XRD indicated that SiO2 in clay reacted with sodium in SCC and formed vitreous analog (Na1.55Al1.55Si0.45O4) to prevent fluoride ion migration and the newly-formed k-Feldspar (K2O.Al2O3.6SiO2) may adsorb fluoride ions in clay-added co-processing. Soluble fluoride NaF in SCC were converted into water-insoluble cuspidine in clay and calcium-added co-processing, in addition to the crystalline phase conversion in clay-added co-processing. Therefore, the risks of finished bricks to human health and the environment were greatly reduced after clay-added or clay and calcium-added treatments.

Solidification/stabilization of spent cathode carbon from aluminum electrolysis by vitric, kaolin and calcification agent: fluorides immobilization and cyanides decomposition.

Spent cathode carbon (SCC) is a hazardous waste containing fluorides and cyanides from aluminum electrolysis. Many literatures have focused on SCC leaching; however, SCC hazard-free treatment remains understudied. This article used 10.0 g raw SCC sample to explore the vitric/kaolin solidification and calcium stabilization of SCC, and analyze their hazard-free mechanisms by the methods of XRD and SEM. The leached fluorides were all below the Chinese identification standard for hazardous wastes (GB5085.3-2007), whether at 750/950 °C for 60 min above 8.0 g vitric, or at 1200 °C for 120 min with above 8.0 g kaolin, or above 700 °C for more than 30 min with above 0.5 g CaCO3. Kaolin/vitric solidification relied on the massive addition of vitric and kaolin to produce glassy or glass-like material (K2O·Al2O3·6SiO2) which may retain fluoride. Calcium stabilization converted soluble fluoride NaF in raw SCC sample into insoluble CaF2. Heating 60 min at 500-1200 °C at oxygen atmosphere decomposed almost of cyanides, with leached cyanides meeting Chinese standard GB5085.3-2007. Mass-loss rates of kaolin addition came from a large amount of adsorbed water and structural water in kaolinite and illite wai lost, and that of CaCO3/CaSO4 addition was attributed to their decomposition into volatile CO2/SO2, while that of CaO was a little negative due to its absorption of water vapor and CO2. In brief, as the effective hazard-free manner of SCC, both kaolin/vitric solidification and calcium stabilization successfully have achieved fluoride immobilization and cyanide decomposition.

Sustainable remediation of dibenzofuran-contaminated soil by low-temperature thermal desorption: Robust decontamination and carbon neutralization.

Thermal desorption (TD) is generally considered to be an effective but unsustainable technology. Decontamination performance, charring behaviors and physicochemical properties during TD of dibenzofuran-contaminated soil (DCS) are explored. After treatment at 300 °C for 20 min, the dibenzofuran concentration decreases from 3969.37 mg/kg to 17.29 mg/kg, lower than Chinese risk screening value. More than 99% of dibenzofuran in soil are removed at low temperature of 300 °C, meanwhile the organic carbon is partially retained in soil. Removal mechanism of DCS at 300 °C is proposed, including desorption, cracking, and charring. Char material of low H:C ratio is produced by the generation, polymerization and dehydrogenation of aromatic intermediates, and then increases carbon stocks and reduces the carbon footprint of contaminated soil. Meanwhile, due to the char generated, pH, cation exchange capacity and specific surface area of DCS heated at 300 °C are higher than those of raw DCS, promoting ecological restoration and enhancing carbon sink in soil ecosystems. The aforesaid saving energy, reducing carbon footprint and enhancing carbon sink are exactly the main innovative technologies for achieving carbon neutrality. Hence, it may be a contribution to climate change mitigation, in addition to a robust and sustainable remediation of organic contaminated soil.

Systematic study on dynamic pyrolysis behaviors, products, and mechanisms of weathered petroleum-contaminated soil with Fe2O3.

Weathered petroleum-contaminated soil (WPCS) with a high proportion of heavy hydrocarbons is difficult to remediate. Our previous research demonstrated that Fe2O3-assisted pyrolysis was a cost-effective technology for the remediation of WPCS. However, the pyrolysis behaviors, products, and mechanisms of the WPCS with Fe2O3 are still unclear. In this study, a combination of Thermogravimetric-Fourier transform infrared spectroscopy (TG-FTIR) and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) techniques were used to explore these pyrolysis characteristics. The thermal desorption/degradation of light and heavy hydrocarbons in the WPCS mainly occurred at 200-400 °C and 400-550 °C, respectively. The activation energy of thermal reaction of heavy hydrocarbons was decreased in the presence of Fe2O3 during the WPCS pyrolysis processes. In the process, the released inorganic gaseous products were mainly H2O and CO2, while the released organic gaseous compounds were primarily cycloalkanes, alkanes, acids/esters, alcohols, and aldehydes. Compared with the WPCS pyrolysis without Fe2O3, the yields of gaseous products released during the WPCS pyrolysis with Fe2O3 were reduced significantly, and some gaseous products were even not detected. This phenomenon was contributed by the following two reasons: 1) heavy hydrocarbons in the WPCS were more easily transformed into coke in the presence of Fe2O3 during pyrolysis; 2) some released gaseous products were reacted with Fe2O3 and fixed on the soil particles. Therefore, the WPCS pyrolysis with Fe2O3 can effectively reduce the burden of tail gas treatment. Criado method analysis results suggested that the reaction mechanism of heavy hydrocarbons during the WPCS pyrolysis with Fe2O3 was rendered as the synergic effects of diffusion, order-based, and random nucleation and growth reactions.