Abnormal eyes and spine development in zebrafish (Danio rerio) embryos and larvae induced by triphenyltin.

Triphenyltin (TPT) is widely used in crop pest control and ship antifouling coatings, which leads to its entry into aquatic environment and poses a threat to aquatic organisms. However, the effects of TPT on the early life stages of wild fish in natural water environments remains unclear. The aim of this study was to assess the toxic effects of TPT on the early life stages of fish under two different environments: field investigation and laboratory experiment. The occurrence of deformities in wild fish embryos and larvae in the Three Gorges Reservoir (TGR) and the developmental toxicity of TPT at different concentrations (0, 0.15, 1.5 and 15 µg Sn/L) to zebrafish embryos and larvae were observed. The results showed that TPT content was higher in wild larvae, reaching 27.21 ng Sn/g w, and the malformation of wild fish larvae mainly occurred in the eyes and spine under natural water environment. Controlled experiment exposure of zebrafish larvae to TPT also resulted in eye and spinal deformities. Gene expression analysis showed that compared with the control group, the expression levels of genes related to eye development (sox2, otx2, stra6 and rx1) and spine development (sox9a and bmp2b) were significantly up-regulated in the 15 µg Sn/L exposure group, which may be the main cause of eye and spine deformity in the early development stage of fish. In addition, the molecular docking results further elucidate that the strong hydrophobic and electrostatic interactions between TPT and protein residues are the main mechanism of TPT induced abnormal gene expression. Based on these results, it can be inferred that TPT is one of the teratogenic factors of abnormal eye and spine development in the early life stage of fish in the TGR. These findings have important implications for understanding the toxicity of TPT on fish.

A systematic comparison of salt removal efficiency in washing treatment by using fly ashes from 13 MSWI plants in China.

Municipal solid waste incineration (MSWI) fly ash contains large amounts of Ca, Si, and other elements, giving it the potential to be used as a raw material for cement production. However, fly ash often contains a high content of salts, which greatly limits its blending ratio during cement production. These salts are commonly removed via water washing, but this process is affected by the nature and characteristics of fly ash. To clarify the influence of the ash characteristics on salt removal, a total of 60 fly ash samples from 13 incineration plants were collected, characterized, and washed. The ash characterization and cluster analysis showed that the incinerator type and flue gas purification technology/process significantly influenced the ash characteristics. Washing removed a high percentage of salts from fly ash, but the removal efficiencies varied significantly from each other, with the chlorine removal efficiency ranging from 73.76% to 96.48%, while the sulfate removal efficiency ranged from 6.92% to 51.47%. Significance analysis further revealed that the salt removal efficiency varied not only between the ash samples from different incinerators, but also between samples collected at different times from the same incinerator. The high variance of the 60 ash samples during salt removal was primarily ascribed to their different mineralogical and chemical characteristics. Mineralogical analysis of the raw and washed ash samples showed that the mineralogical forms and proportion of these salts in each ash sample greatly influenced their removal. The presence of less-soluble and insoluble chloride salts (e.g., CaClOH, Ca2Al(OH)6(H2O)2Cl etc.) in fly ash significantly affected the chlorine removal efficiency. This study also found that Fe, Mn, and Al in fly ash were negatively correlated with the dechlorination efficiency of fly ash. In summary, the different physical and chemical properties of fly ash caused great discrepancies in salt removal. Consequently, it is suggested to consider the potential impact of the ash source and ash generation time on salt removal to ensure a reliable treatment efficiency for engineering applications.

Simulating CH4 emissions from MSW landfills in China from 2003 to 2042 using IPCC and LandGEM models.

Anaerobic landfills have long been the primary means of municipal solid waste (MSW) disposal in China. Landfills are the third largest emission source of methane (CH4), which is the second most abundant greenhouse gas in the atmosphere and has a high greenhouse effect. To date, there have been no reliable model predictions of long-term CH4 emissions from landfills in China. In this study, two general models, IPCC and LandGEM, were introduced to simulate CH4 emissions from all landfills in China. By comparing the results of the Shuangkou landfill in Tianjin with the default and local parameters, the local parameters were fixed to simulate landfill CH4 emissions in 31 regions over 40 years (2003-2042). The MSW landfills were obtained from statistical data for 18 years (2003-2020). The total emissions in China predicted by LandGEM and IPCC were 2.42 E+07 Mg and 2.36 E+07 Mg, respectively. These data provide a reliable reference for determining the long-term CH4 emissions from landfills in China.

Enhanced removal of metal-cyanide complexes from wastewater by Fe-impregnated biochar: Adsorption performance and removal mechanism.

Metal-cyanide complexes are common contaminants in industrial wastewater. Removal of these refractory contaminants is essential before their discharge into the environment. This study investigated a biochar (BC)-based sorbent material that could be applied for the efficient removal of metal-cyanide complexes from wastewater. In consideration of the strong electrostatic repulsion of the pristine BC toward anions, iron-modified BC (Fe-BC) composites were fabricated by a one-step co-pyrolysis of corn straw and FeCl3 at 600-800 °C. The adsorption performance and corresponding sorption mechanisms of representative metal-cyanide complexes (ferricyanide [Fe(CN)6]3- and tetracyanonickelate [Ni(CN)4]2-) onto the Fe-BC composites were investigated. The results indicated that the Fe-BC composites had significantly high affinity toward the metal-cyanide complexes, reaching a maximum sorption capacity of 580.96 mg/g for [Fe(CN)6]3- and 588.86 mg/g for [Ni (CN)4]2-. A mechanistic study revealed that Fe-impregnation during BC fabrication could effectively alter the negatively charged BC surface, forming more functional groups that could interact with the metal-cyanide complexes. Moreover, the transformation of carbon structure promoted the carbothermal reduction process, leading to the formation of various reductive-Fe minerals in the resulting Fe-BC composites. These modification-induced alterations to the surface and structural characteristics of BC were expected to facilitate the adsorption/precipitation of target contaminants. Different sorption mechanisms were proposed for the two metal-cyanide complexes that were the focus of this study. For [Fe(CN)6]3-, precipitation by Fe-bearing species in the Fe-BC composites was the major factor controlling [Fe(CN)6]3- removal, while for [Ni(CN)4]2- hydrogen bonding interactions between surface functional groups (especially hydroxyl (-OH) and carboxyl (-COOH)) and [Ni(CN)4]2- were the main factors controlling removal.

Removal of harmful components from MSWI fly ash as a pretreatment approach to enhance waste recycling.

Municipal solid waste incineration (MSWI) fly ash contains many harmful components that may limit its potential for recycling. An effective pretreatment is therefore required before any recycling can be implemented. In this study, the effects of four pretreatment methods (water washing, CO2-aided washing, CO32--aided washing, and CO2 and CO32--aided washing) on the extraction behavior of chloride, sulfate, and heavy metals were evaluated. Water washing was found to be effective for the extraction of all easily and moderately soluble Cl-bearing salts, achieving Cl extraction ratios of 88%, 90%, and 96% for ash from Chongqing (CQ), Qingdao (QD), and Tianjin (TJ), respectively. Injection of CO2 during washing facilitated decomposition of the hardly soluble Cl-bearing salts, increasing the Cl extraction efficiency by 6% for CQ ash and 9% for QD ash. However, for the TJ ash that contained few insoluble Cl-bearing minerals, CO2 injection decreased the Cl extraction rate. The addition of CO32- had a negative influence on Cl extraction for all ashes, but it slightly promoted sulfate extraction. Despite the high Cl removal rate, only 23-37% of the sulfate and 0.1-12% of heavy metals were removed. Overall, water-based pretreatment, especially CO2-aided washing, significantly altered the physical, chemical, and mineralogical characteristics of the fly ash, making it more suitable for recycling. Consequently, the blending ratio of the fly ash for cement clinker manufacture increased from 0.2 to 0.3% in the raw ash to 3.5-5.5% in the treated ash, enabling the extensive use of ash materials.

Effectiveness and mechanism of cyanide remediation from contaminated soils using thermally activated persulfate.

Persulfate (PS)-based advanced oxidation processes have been frequently employed for contaminant remediation, but the effectiveness of PS oxidation for the elimination of cyanide-bearing contaminants from soil, and the underlying mechanisms, have rarely been explored. This study investigated the degradation of two iron-cyanide (Fe-CN) complexes (ferricyanide and ferrocyanide) with thermally activated PS via two remediation strategies, namely one-step oxidation (direct PS oxidation) and two-step oxidation (alkaline extraction followed by PS oxidation). The two-step oxidation process was more effective for the elimination of cyanide pollutants from soil, reaching >94% remediation efficiency for both Fe-CN complexes studied. The presence of dissolved soil components, especially soil organic matter, increased consumption of PS during the remediation process. A combined analysis based on electron paramagnetic resonance (EPR), free radical scavenging, and degradation product identification revealed that SO4- and HO were the principal reactive radicals responsible for Fe-CN degradation. Based on the determination of radical species and identification of decomposition products, a transformation pathway for Fe-CN complexes during thermally activated PS oxidation is proposed. Overall, this study demonstrates the effectiveness of the thermally activated PS oxidation technique for cyanide elimination from polluted soil. Further study is required to verify the feasibility of this method for field applications.

Comprehensive reutilization of iron in iron ore tailings: preparation and characterization of magnetic flocculants.

A large number of iron ore tailings (IOTs) are produced in steel industry, posing threat to the environment during its storage and disposal. To effectively reutilize Fe in IOTs, we propose a comprehensive utilization scheme: (1) most Fe in IOTs is extracted by concentrated hydrochloric acid to form FeCl3 flocculants; (2) after separation from the FeCl3 flocculants, a small amount of Fe is absorbed on the residue solids, which is further washed out to synthesize micron Fe3O4 as magnetic seeds. Results show that the as-synthetic FeCl3 flocculants meet the product standard for FeCl3 flocculants in China (GB/T 4482-2018) after a series of treatments including rotary evaporation, neutralization, and dilution and have comparable performance with commercial polyaluminum chloride (PAC) and polyaluminum ferric chloride (PAFC). Moreover, the addition of synthetic superparamagnetic Fe3O4 (as magnetic seeds) doubled the flocculation rate compared with as-synthetic FeCl3 flocculants alone. Finally, the reutilization of Fe in IOTs can create a direct economic value of ¥ 1.27/kg IOTs, and produce 745 g high-silicon residues for further reutilization, which indicates that our comprehensive utilization scheme is of great application potential.

Remediation of hexavalent chromium in contaminated soil using amorphous iron pyrite: Effect on leachability, bioaccessibility, phytotoxicity and long-term stability.

A large amounts of arable land is facing a high risk of hexavalent chromium (Cr(VI)) pollution, which requires remediation using a low toxic agent. In this study, the remediation effect of amorphous iron pyrite (FeS2(am)) on Cr(VI) in Cr(VI)-contaminated soil was evaluated by systematically analyzing the variation of the leachability, bioaccessibility, phytotoxicity, and long-term stability of the remediated soil. The effectiveness of FeS2(am) on the leachability was assessed by alkaline digestion and the toxicity characteristic leaching procedure (TCLP); the effect on the bioaccessibility was evaluated via the physiologically based extraction test (PBET) and the Tessier sequential extraction; the effect on the phytotoxicity was assessed via phytotoxicity bioassay (seed germination experiments) based on rape (Brassica napus L.) and cucumber (Cucumis Sativus L.), and the long-term stability of the Cr(VI)-remediated soil was appraised using column tests with groundwater and acid rain as the influents. The results show that FeS2(am), with a stoichiometry of 4× exhibited a high efficiency in the remediation of Cr(VI) and decreased its leachability and bioaccessibility during the 30-day remediation period. In addition, seed germination rate, accumulation and translocation of Cr, and root and shoot elongation of rape and cucumber of remediated soil are not significantly different from those of clean soil, illustrating that FeS2(am) is suitable for remediating Cr(VI) contaminated arable soil. The stabilization of Cr(VI) in contaminated soil using FeS2(am) was maintained for 1575 days. The long-term effectiveness was further confirmed by the increasing amount of free Fe and Mn in the effluent and the decreasing redox potential. In summary, FeS2(am) has an excellent efficiency for the remediation of Cr(VI), demonstrating it is a very promising alternative for use in the contaminated arable soil.

Thermal remediation of cyanide-contaminated soils：process optimization and mechanistic study.

Site soils with persistent cyanide compounds (primarily iron-cyanide complex) pose potential hazards to the environment and require remediation before redevelopment. This study evaluated the possibility of thermal treatment on remediation of cyanide-contaminated soils via batch heating experiments spanning a wide temperature range (200-500 °C). The change with operation variables of total cyanide and some reaction intermediates (e.g. CN-) was analyzed in order to elucidate the optimal variables that guarantee cyanide removal while generating no hazardous byproducts. Temperature, heating time and cyanide species have been found to be important parameters influencing removal/destruction of cyanide in soils. For soils bearing K3[Fe(CN)6] and K4[Fe(CN)6], a removal efficiency of >99.9% can be obtained with temperatures over 350 °C at 1 h, while for samples bearing Fe4[Fe(CN)6]3, a higher temperature (>450 °C) is needed to obtain an equivalent efficiency. During heating, the iron-cyanide complexes decomposed, releasing highly toxic free cyanides, which will subsequently be oxidized. However, a small percentage of free cyanide can always be detected as a result of incomplete oxidation, thus caution should be taken to minimize the accumulation of free cyanide during thermal treatment.

Separation and characterization of magnetic fractions from waste-to-energy bottom ash with an emphasis on the leachability of heavy metals.

Magnetic fractions were extracted from pulverized waste-to-energy (WTE) bottom ashes using a combined wet-dry extraction method. The resulting magnetic and non-magnetic fractions were subjected to compositional, mineralogical, and redox state analyses by X-ray diffraction (XRD), X-ray fluorescence, and X-ray photoelectron spectroscopy (XPS), respectively. The distribution and leaching toxicity of heavy metals were assessed to evaluate potential effects on the environment. Compositional analyses revealed that Fe accounted for 35% of the magnetic fraction of pulverized ashes, which was approximately seven times that of the raw ash. In addition to Fe, elemental Ni, Mn, and Cr were also significantly enriched in the magnetic fractions. The mineralogical analysis determined that Fe was primarily present as hematite and magnetite, and metallic iron was also identified in the magnetic fraction samples. The XPS analysis further proved the existence of zero-valence Fe. However, a significant amount of Fe remained in the non-magnetic fractions, which could partially be ascribed to the intergrowth structure of the various minerals. The elevated concentrations of toxicity characteristic leaching procedure (TCLP)-extracted Mn, Ni, Cr, Cu, Pb, and Zn were primarily ascribed to the lower buffering capability of the magnetic fractions, with the enrichment of Mn, Ni, and Cr in the magnetic fractions also contributing to this elevation.

Heavy metals in sediments, soils, and aquatic plants from a secondary anabranch of the three gorges reservoir region, China.

We investigated the occurrence of cadmium (Cd), copper (Cu), chromium (Cr), nickel (Ni), lead (Pb), Znic (Zn), iron (Fe), manganese (Mn), and magnesium (Mg) in sediments, as well as in related soils and aquatic plants in the Liangtan River, a typical secondary anabranch of the Yangtze River in the Three Gorges Reservoir Region (TGRR) of China. We found that sediments accumulated more metals than soils and aquatic plants. Concentrations of the nine metals in sediments and soils followed the same sequence, while their concentrations in aquatic plants followed a different sequence. Potential adverse effects of contaminated sediments on benthic fauna were evaluated, and the results showed that the toxic effect on benthic organisms followed the sequence Zn > Ni > Cr > Cu > Cd > Pb. The potential ecological risk index analysis indicated that Cd in sediments had considerable ecological risk, whereas Cr, Cu, Zn, Ni, and Pb had low ecological risk. The potential ecological risk index (RI) of the heavy metals in sediments of the Liangtan River was 174.9, indicating moderate ecological risk. The transfer factor trend of metals for aquatic plants showed that Cd and Ni had the most and least accumulation, respectively. For Cu, Cd, Mg, Pb, and Cr, a significant positive correlation of the metal concentrations was observed between sediments and soils, but no correlations (excluding Cr) were detected between sediments and aquatic plants. Our study indicated that anthropogenic input may be the primary source of metal contamination in the Liangtan River, and that Zn and Cd pollution in the Liangtan River should be further explored.

Occurrence of organotin compounds in river sediments under the dynamic water level conditions in the Three Gorges Reservoir Area, China.

The Three Gorges Project is the largest hydro project in the world, and the water level of the Three Gorges Reservoir (TGR) is dynamic and adjustable with the aim of flood control and electrical power generation. It is necessary to investigate the pollutants and their underlying contamination processes under dynamic water levels to determine their environmental behaviors in the Three Gorges Reservoir Area (TGRA). Here, we report the assessment of organotin compounds (OTs) pollution in the river sediments of the TGRA. Surface sediment samples were collected in the TGRA at low and high water levels. Tributyltin (TBT), triphenyltin (TPhT), and their degradation products in sediments were quantified by gas chromatography-mass spectrometry. Butyltins (BTs) and phenyltins (PhTs) were detected in sediments, and BTs predominated over PhTs in the whole study area under dynamic water level conditions. The concentrations of OTs in sediments varied markedly among locations, and significant concentrations were found in river areas with high levels of boat traffic and wastewater discharge. Sediments at all stations except Cuntan were lightly contaminated with TBT, and total organic carbon (TOC) was a significant factor affecting the fate of TBT in the TGRA. The butyltin and phenyltin degradation indices showed no recent inputs of TBT or TPhT into this region, with the exception of fresh TPhT input at Xiakou Town. Shipping activity, wastewater discharge, and agriculture are the most likely sources of OTs in the TGRA.

Early warning indicators for monitoring the process failure of anaerobic digestion system of food waste.

To determine reliable state parameters which could be used as early warning indicators of process failure due to the acidification of anaerobic digestion of food waste, three mesophilic anaerobic digesters of food waste with different operation conditions were investigated. Such parameters as gas production, methane content, pH, concentrations of volatile fatty acid (VFA), alkalinity and their combined indicators were evaluated. Results revealed that operation conditions significantly affect the responses of parameters and thus the optimal early warning indicators of each reactor differ from each other. None of the single indicators was universally valid for all the systems. The universally valid indicators should combine several parameters to supply complementary information. A combination of total VFA, the ratio of VFA to total alkalinity (VFA/TA) and the ratio of bicarbonate alkalinity to total alkalinity (BA/TA) can reflect the metabolism of the digesting system and realize rapid and effective early warning.

Geoenvironmental weathering/deterioration of landfilled MSWI-BA glass.

Municipal solid waste incineration bottom ash (MSWI-BA) glass serves as a matrix of assorted bottom ash (BA) compounds. Deterioration of the BA glass phases is quite important as they regulate the distribution of a series of toxic elements. This paper studied landfilled MSWI-BA samples from the mineralogical and geochemical viewpoint to understand the deterioration behavior of the BA glass phases as well as mechanisms involved. Bulk analysis by PXRD as well as micro-scale analysis by optical microscopy and SEM/EDX was conducted for such purposes. The results revealed that dissolution of the BA glass phases has resulted in a deterioration layer of 10(0)-10(2)µm thickness after years of disposal. This rapid weathering process is highly relevant to the specific glass characteristics and solution pH. The BA glass phases with more embedded compounds and cracks/fissures tend to be more vulnerable. Moreover, the generally alkaline pH in ash deposit favors a rapid disruption of the glass phase. The weathering products are mainly gel phases (including Al-Si gel, Ca-Al-Si gel, Fe-Al-Si gel etc.) with iron oxide/hydroxide as accessory products. Breakdown of the BA glass phases triggers chemical evolution of the embedded compounds. Based on all the findings above, a model is proposed to illustrate a general evolution trend for the landfilled MSWI-BA glass phases.

Impacts of natural weathering on the transformation/neoformation processes in landfilled MSWI bottom ash: a geoenvironmental perspective.

UNLABELLED: Natural weathering processes are significant mechanisms that noticeably affect the fundamental nature of incineration ash residues. To provide a greater understanding of these processes, a MSWI (mono)landfill site in the north east of the US was selected as the target for systematic investigation of the natural weathering of bottom ash residues. Samples of various ages were collected from locations A (1 yr), B (10 yrs), C (13-14 yrs) and D (20 yrs) of the landfill in 2009. We investigated the phase transformation of the collected bottom ash particles, neoformation processes as well as the behavior and distribution of certain heavy metals (Cu, Pb, Zn, Ni, and Cr) in the neoformed phases using optical microscopy, SEM-EDX, and bulk examinations. KEY FINDINGS: at the preliminary stage, the waste metallic particles (Al, Fe, and Cu) and unstable minerals such as lime, portlandite, ettringite and hydrocalumite convert to oxide and hydroxide (hydrate) phases, calcite, alumina gel and gypsum. At the intermediate stage, the decomposition of melt products including magnetite spinels and metallic inclusions is triggered due to the partial dissolution of the melt glass. At the longer time horizon it is possible to track the breakdown of the glass phase, the extensive formation of calcite and anhydrite, Al-hydrates and more stable Fe-hydrates all through the older ash deposits. Among the dominant secondary phases, we propose the following order based on their direct metal uptake capacity: Fe-hydrates>Al-hydrates>>calcite. Calcite was found to be the least effective phase for the direct sorption of heavy metals. Based on overall findings, a model is proposed that demonstrates the general trend of ash weathering in the landfill.

Alteration of municipal solid waste incineration bottom ash focusing on the evolution of iron-rich constituents.

Municipal solid waste incineration (MSWI) bottom ash contains a considerable amount of Fe-rich constituents. The behaviors of these constituents, such as dissolution and precipitation, are quite important as they regulate the distribution of a series of ions between the liquid (percolated fluid) and solid (ash deposit) phases. This paper studied both fresh and weathered MSWI bottom ash from the mineralogical and geochemical viewpoint by utilizing optical microscopy, scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), and powder X-ray diffraction. The analysis results revealed that for the fresh bottom ash, iron preferentially existed in the chemical forms of spinel group (mainly Fe(3)O(4), and a series of Al- or Ti- substituted varieties), metallic inclusions (including Fe-P, Fe-S, Fe-Cu-Pb), hematite (Fe(2)O(3)) and unburned iron pieces. In the 1-20 years weathered bottom ash collected from a landfill site, interconversions among these Fe-rich constituents were identified. Consequently, numerous secondary products were developed, including goethite (α-FeOOH), lepidocrocite (γ-FeOOH), hematite, magnetite, wustite (FeO), Fe-Si-rich gel phase. Of all these transformation products, hydrous iron oxides were the most common secondary minerals. Quantitative chemical analysis of these secondary products by SEM/EDX disclosed a strong association between the newly formed hydrous iron oxides and heavy metals (e.g. Pb, Zn, Ni, and Cu). The results of this study suggest that the processes of natural weathering and secondary mineralization contribute to reduction of the potential risks of heavy metals to the surrounding environments.

Mineralogical characterization of municipal solid waste incineration bottom ash with an emphasis on heavy metal-bearing phases.

Municipal solid waste incineration (MSWI) bottom ash contains a considerable amount of heavy metals. The occurrence and uneven distribution of these heavy metals in bottom ash can increase the complexity of such residues in terms of long-term behavior upon landfilling or recycling. Bottom ashes sampled from three stoker-type incinerators in Japan were analyzed in this paper. This study presents detailed information on the mineralogical characterization of bottom ash constituents and the weathering behavior of these constituents by means of optical microscopy and scanning electron microscopy. It was revealed that bottom ash mainly consists of assorted silicate-based glass phases (48-54 wt% of ash) and mineral phases including melilites, pseudowollastonite, spinels, and metallic inclusions (Fe-P, Fe-S, Fe-Cu, Cu-Sn, Cu-Zn, Cu-S, and Cu-Pb dominated phases), as melt products formed during the incineration process. The compounds embedded in the glass matrix, e.g. spinels and metallic inclusions, played the most important role in concentration of heavy metals (Pb, Zn, Cu, Cr, Mn, Ni, etc.). Other phases such as refractory minerals and ceramics, frequently found in ash, were of less significance in terms of their influence on the involvement of heavy metals. Analysis of lab-scale artificially weathered and 10-year landfilled bottom ash samples revealed that secondary mineralization/alteration of the bottom ash constituents principally carbonation and glass evolution substantially decreased the potential risk of the heavy metals to the surrounding environment.