化学老化后稻壳生物炭理化性质的改变及微观结构表征

为研究化学老化对生物炭理化性质与微观结构的影响,本研究采用H_2O_2、HNO_3老化不同温度(350℃和550℃)下制备的稻壳生物炭,并利用元素分析、扫描电镜、漫反射红外光谱、X射线光电子能谱等测定比较生物炭老化前后表面理化性质及微观结构的变化.结果表明,经两种氧化剂老化后两种生物炭中O元素含量及O/C原子比均增加.与老化前生物炭相比,老化后两种生物炭中羟基、羧基、酮羰基、脂肪醚、酯基等含氧官能团的含量均发生不同程度的变化.通过漫反射红外与X射线光电子能谱分析相结合,发现两种稻壳生物炭经H_2O_2、HNO_3老化后均生成了羟基、羧基等含氧官能团,从而使得生物炭极性增加.此外,经HNO_3老化后稻壳炭表面生成硝基、硝酸盐等含氮基团,N元素含量亦显著增加.但氧化剂对两种温度下制备的生物炭中炭元素含量影响存在差异:经H_2O_2、HNO_3氧化后550℃制备的生物炭(R550)中C元素含量与芳香性降低;而经H_2O_2氧化后,350℃制备的生物炭(R350)中C元素含量与芳香性均上升.     

磷酸改性生物炭-LDHs(Mg-Al-NO3)复合材料对双酚A的吸附

本研究选取油菜秸秆为原料,在600℃下热解得到生物炭和磷酸改性生物炭,并用共沉淀法制备3种改性生物炭-LDHs(Mg-Al-NO_3)复合材料.采用批量吸附法研究不同pH、吸附时间和不同生物炭/LDHs配比条件下复合材料对双酚A的吸附特性,借助XRD、FTIR和BET等测试手段探究了复合材料吸附双酚A的机制.结果表明,改性生物炭-LDHs(Mg-Al-NO_3)复合材料吸附双酚A的吸附平衡时间为4 h,符合准二级动力学方程(R~20.99);复合材料对双酚A的吸附效果稍逊于改性生物炭,改性生物炭在复合材料中所占比重越大,吸附效果越好.当pH值在5.0—9.0范围内变化时,改性生物炭-LDHs(Mg-Al-NO_3)复合材料对双酚A的吸附量呈下降趋势,且在pH=9.0时达到最小值.等温吸附模型数据表明,复合材料用Freundlich等温吸附模型效果更好.通过XRD、BET、FTIR测试研究发现,由于LDHs占据了生物炭表面的活性位点,致使生物炭与双酚A之间的相互作用减弱,降低了复合物的吸附能力.本研究结果初步阐释了改性生物炭-LDHs(Mg-Al-NO_3)复合材料吸附双酚A的机理,为生物炭-LDHs复合材料处理水体中有机污染物的应用提供了借鉴和参考.     

模拟生物质炭老化前后对菲吸持作用的影响

通过实验室培养实验模拟生物质炭的老化过程,探索不同材料制备的生物质炭老化前后对多环芳烃(菲)吸持作用的影响,利用扫描电镜与傅里叶变化红外光谱等技术探究生物质炭老化前后的结构变化.结果表明,生物质炭老化过程中会形成老化层,550℃热解条件下,两种材料制备的生物质炭老化后含氧量增加、CEC增加,对菲的吸附能力均增强,主要与老化后表面羧基减弱和脂肪族官能团增加有关,而老化后稻壳炭的吸附能力更强与醚键的显著增加有关.     

生物炭基针铁矿复合材料对水中莠去津吸附特性研究

以牛粪和水稻秸秆为原料,分别在300℃和500℃条件下制备生物炭,同时通过共沉淀方法制备生物炭基针铁矿复合材料,研究生物炭及生物炭基复合材料对水中莠去津吸附特征。SEM和XRD分析结果表明,复合材料表面粗糙程度增加,2θ在21.2°、33.4°、36.6°、47.6°处出现针铁矿的特征衍射峰,生物炭基针铁矿复合材料制备成功。通过对吸附动力学和等温吸附平衡分析发现,生物炭对莠去津的吸附行为更符合准二级动力学方程,等温吸附过程符合Freundlich模型(r~2为0.925—0.996)。在25℃条件下,莠去津在300℃和500℃条件下制备的针铁矿负载牛粪生物炭上的吸附量分别是原生物炭上吸附量的1.59倍和2.99倍,在针铁矿负载水稻秸秆生物炭上的吸附量分别是原生物炭上吸附量的2.02倍和1.73倍。比表面积和孔结构数据显示,生物炭基复合材料的比表面积是原生物炭材料的4.41—20.8倍,制备生物炭材料的孔结构以中孔为主。莠去津在生物炭上的吸附大体表现为吸热的自发过程。对不同材料制备的生物炭及与生物炭基复合材料吸附性能进行对比,结果表明水稻秸秆制备的生物炭对莠去津的吸附性能优于牛粪制备的生物炭,生物炭基针铁矿复合材料对莠去津的吸附效果优于原生物炭。随制备温度的升高,相同材料生物炭对莠去津吸附性能略有增加。研究结果可为生物炭及生物炭基针铁矿复合材料去除水中莠去津的应用提供理论依据。     

花生壳和松木屑制备的生物炭对Cu~(2+)的吸附研究

为了深入了解生物炭施用对重金属环境行为和风险的影响,研究了生物炭吸附Cu~(2+)的机理。以花生壳和松木屑为原料,采用限氧升温炭化法,在200~500℃热裂解制得8种生物炭,并通过元素分析仪、傅立叶变换红外光谱分析(FITR)和扫描电镜-能谱分析(SEM/EDS)对其进行了表征。同时,采用批试验方法研究了生物炭对Cu~(2+)吸附行为。研究结果表明,(1)热解温度越高,灰分含量越多,p H增大,生物炭芳构化程度越高,比表面积更大;(2)Cu~(2+)在生物炭上的吸附动力学划分为快吸附和慢吸附两个一级动力学阶段,其中快室是生物炭表面含氧官能团如羧基(-COOH)、酚羟基(-OH)等与重金属离子相互作用的吸附,慢速室是生物炭通过颗粒内扩散作用被生物炭吸附;(3)FM模型更适合于对花生壳和松木屑制备的生物炭吸附Cu~(2+)的数据进行拟合,所得非线性指数(n)的值在0.23~0.67之间且随热解温度升高n值越来越小;(4)在热解温度为200~500℃,花生壳生物炭对Cu~(2+)的吸附量先下降后增加且PS5对Cu~(2+)的吸附性能最佳;而松木生物炭对Cu~(2+)的吸附量没有明显的规律性变化,但PC2对Cu~(2+)的吸附性能最佳。     

滇池沉积物生物炭的热稳定性及化学稳定性特征

在200和500℃制备滇池沉积物(泥炭土和草海底泥)生物炭,采用热重分析法和氧化剂氧化法,分别研究其热稳定性和化学稳定性,为判断沉积物生物炭的寿命、指导其应用提供数据和理论基础.研究显示,泥炭土和草海底泥中有机组分的损失主要发生在500℃烧制过程(分别为40%和30%);泥炭土和草海底泥热解后灰分含量分别从44.35%、58.25%升高到58.78%、70.05%(500℃),且脂肪性减弱而芳香性增强.随烧制温度提高,碳结构更加致密,沉积物生物炭热稳定性显著提高.不同温度生物炭的化学稳定性未表现出明显差异,是因为大量的灰分对有机组分提供了较强的保护作用,致使原料和低温生物炭也具有较强的化学稳定性.草海底泥及其生物炭因为灰分含量较高、芳香性较强,热稳定性高于泥炭土.本研究指出,沉积物生物炭稳定性规律不同于传统生物质生物炭,灰分可以明显提高生物炭抵抗环境老化的能力.     

生物炭的老化及其对温室气体排放影响的研究进展

生物炭是生物质在无氧或限氧条件下经高温热解后产生的多孔富碳物质,其被广泛施加到土壤中改良土壤性质,调节温室气体排放。生物炭施入土壤后,长期受外界物理、化学和生物等环境作用导致生物炭性质发生缓慢改变,这个过程称为生物炭的老化。文章综述了原位生物炭自然老化和实验室模拟老化的方法以及老化后生物炭理化性质的变化,从理化性质变化的角度论述了生物炭老化过程对二氧化碳(CO_2)、甲烷(CH_4)和氧化亚氮(N_2O)这3种温室气体排放的影响,并初步解释生物炭老化过程对增加或减少温室气体排放的可能机制。主要内容如下:生物炭老化方法可以分为自然老化和人工模拟老化,模拟老化方法包括生物、物理和化学老化。生物炭发生老化后,生物炭的比表面积(SSA)和孔容根据老化强度而有不同变化,自然或人工模拟的温和老化方法使生物炭表面上有新的纳米微孔生成,生物炭SSA增加,而使用强酸或强氧化剂的强烈老化方式可破坏生物炭孔隙结构,导致SSA和孔容下降。从化学性质方面来讲,生物炭C/N比随老化过程而降低,但是O/C比却随老化过程而升高;此外,当生物炭老化时,生物炭表面含氧官能团增加,例如羧基、羰基和酚基等,这些含氧基团可以和阳离子结合形成羧酸盐和酚盐,同时释放H~+,导致老化生物炭的pH值降低。基于有限的研究报道,老化生物炭仍然具有一定的CH4减排潜力,这得益于土壤通气状态的改善和甲烷氧化菌氧化CH_4潜力提升。相反,由于生物炭极性增强和pH值降低,生物炭老化过程有促进土壤有机质矿化增加CO_2和N_2O排放的趋势。然而为了辅正这一论断,准确评估生物炭老化的环境效应,长期原位生物炭老化并同时设置新鲜生物炭对照的研究需要进一步开展,以探明生物炭老化过程对温室气体排放的影响机制,为生物炭生产和合理施用提供科学应用指导。     

农林废弃物生物炭钝化典型土壤重金属的机制研究进展

土壤重金属污染成为食品安全的重大隐患,农林废弃物生物炭来源广泛,成本低,已被广泛用于土壤重金属污染修复。本文综述了农林废弃物生物炭的制备方法及影响其性能的关键因素,并重点探讨了利用农林废弃物生物炭钝化土壤典型重金属的作用机制。发现木质、竹、秸秆、稻壳和动物粪便等材料被广泛用于生物炭制备,热解温度、热解停留时间以及原材料种类均会影响生物炭的性能,其中植物生物炭比表面积的增加、吸附性能和重金属固定性能的提高均高于牛粪生物炭,在300℃高温热解制得的生物炭含有更多的含氧官能团,而在500～700℃高温热解制得的生物炭含有更多的微孔和更大的表面积,高热解温度下适当的停留时间有助于生物炭结构的形成。此外,生物炭还可以影响土壤微生物的多样性和种类来提高吸附能力,通过络合沉淀固定汞(Hg)、镉(Cd)和铜(Cu),通过静电吸附、络合作用和阳离子交换来固定铬(Cr)、砷(As)、锌(Zn)和铅(Pb)。最后,为确保生物炭的安全生产和可持续利用提出了未来的研究方向。     

氧氟沙星和诺氟沙星在磷酸改性生物炭上的等温吸附行为

本研究考察了不同制备温度下(200℃、350℃、500℃、650℃),磷酸改性前后生物炭的理化性质,及其对氧氟沙星(OFL)和诺氟沙星(NOR)的等温吸附行为.采用N2物理吸附、扫描电镜、热重及元素分析等表征,对离子型抗生素在磷酸改性的生物炭上的等温吸附行为进行了研究.结果表明,随着制备温度的增加,改性生物炭的总孔体积不断增大,孔隙结构广泛形成,比表面积急剧增加.磷酸改性有助于提高生物炭的产率以及保留生物炭的极性官能团.OFL和NOR在改性生物炭上的吸附显著高于原始生物炭,且350℃下制备的改性生物炭具有最大吸附量,其吸附机制归因于吸附剂的大比表面积和孔隙填充作用.由于孔隙的利用率降低和炭的疏水性增强,OFL和NOR在更高温度改性生物炭上的吸附量逐渐降低.因此,在处理以上两种污染物时,350℃可作为磷酸改性生物炭的最佳裂解温度,且有利于减少能耗,节约资源.     

老化作用对水稻秸秆生物炭吸附Cd(Ⅱ)能力的影响

环境变化使生物炭材料发生老化作用,老化后的生物炭是否仍具有较强的吸附能力是评价生物炭对Cd修复的长期稳定性的重要指标.本文采用自然老化(Spontaneous aging,SPON),冻融循环老化(Freeze-thaw cycles aging,FTC)和高温老化(High temperature aging,HT)的方法对水稻秸秆生物炭进行2个月的人工加速老化,运用扫描电镜(SEM-EDS)、元素分析仪、傅里叶红外光谱分析仪(FTIR)研究老化作用对秸秆生物炭材料的影响,再通过等温吸附实验研究生物炭老化前后对Cd吸附性能特征的变化.结果表明,老化作用使生物炭材料局部发生破碎,增加了生物炭表面O/C比.老化作用显著影响秸秆生物炭表面的官能团,降低了生物炭表面—OH的数量,增加了CO、—COOH和Si—O—Si的数量,出现了C≡C键,可为Cd提供更多的吸附位点.等温吸附试验进一步证明了老化后的生物炭提高了对Cd(Ⅱ)的吸附性能.与生物炭原样相比,冻融循环老化、高温老化、自然老化使生物炭的Cd最大吸附量分别达到了26.49、33.30、23.40 mg·g~(-1),增加了27.8%,60.7%,12.9%.本研究表明老化作用改变了生物炭材料的表观结构和官能团,增强了对Cd(Ⅱ)的吸附能力,因此生物炭对Cd的修复具有一定的长期稳定性.     

Sorption of phenanthrene to biochar modified by base

Biochar (BC) is a potential material for removal of polycyclic aromatic hydrocarbons from soil and water, and base modification is a promising method for improving its sorption ability. In this study, we synthesized a series of base-modified biochars, and evaluated their sorption of phenanthrene. Original biochars were produced by pyrolysis of three feedstocks (rice straw, wood and bamboo) at five temperatures (300°C, 350°C, 400°C, 500°C and 700°C). Base-modified biochars were further obtained by washing of biochars with base solution. The base soluble carbon (SC) was extracted from the supernatant, which were only obtained from biochars pyrolyzed at low temperatures (<500°C) and the content was decreased with the increase of pyrolysis temperature. The SC content between different feedstocks followed the trend of rice straw>wood>bamboo when same pyrolysis conditions were applied. It was found that base modification improved the sorption of phenanthrene on biochars that SC could be extracted from (extractable-BCs). However, base treatment but had limited effects for biochars that no SC could be extracted from. It suggested that base modification improved the sorption of phenanthrene to extractable-BCs by removing the SC and thus increasing the surface area and hydrophobicity. Therefore, base modification was suggested to be used in modifying extractable-BCs.

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Efficacy of woody biomass and biochar for alleviating heavy metal bioavailability in serpentine soil

Crops grown in metal-rich serpentine soils are vulnerable to phytotoxicity. In this study, Gliricidia sepium (Jacq.) biomass and woody biochar were examined as amendments on heavy metal immobilization in a serpentine soil. Woody biochar was produced by slow pyrolysis of Gliricidia sepium (Jacq.) biomass at 300 and 500 °C. A pot experiment was conducted for 6 weeks with tomato (Lycopersicon esculentum L.) at biochar application rates of 0, 22, 55 and 110 t ha^?1. The CaCl₂ and sequential extractions were adopted to assess metal bioavailability and fractionation. Six weeks after germination, plants cultivated on the control could not survive, while all the plants were grown normally on the soils amended with biochars. The most effective treatment for metal immobilization was BC500-110 as indicated by the immobilization efficiencies for Ni, Mn and Cr that were 68, 92 and 42 %, respectively, compared to the control. Biochar produced at 500 °C and at high application rates immobilized heavy metals significantly. Improvements in plant growth in biochar-amended soil were related to decreasing in metal toxicity as a consequence of metal immobilization through strong sorption due to high surface area and functional groups.     

Ammonia and phosphorus removal from agricultural runoff using cash crop waste-derived biochars

• Orange tree residuals biochar had a better ability to adsorb ammonia. • Modified tea tree residuals biochar had a stronger ability to remove phosphorus. • Partially-modified biochar could remove ammonia and phosphorus at the same time. • The real runoff experiment showed an ammonia nitrogen removal rate of about 80%. • The removal rate of total phosphorus in real runoff experiment was about 95%. Adsorption of biochars (BC) produced from cash crop residuals is an economical and practical technology for removing nutrients from agricultural runoff. In this study, BC made of orange tree trunks and tea tree twigs from the Laoguanhe Basin were produced and modified by aluminum chloride (Al-modified) and ferric sulfate solutions (Fe-modified) under various pyrolysis temperatures (200°C–600°C) and residence times (2–5 h). All produced and modified BC were further analyzed for their abilities to adsorb ammonia and phosphorus with initial concentrations of 10–40 mg/L and 4–12 mg/L, respectively. Fe-modified Tea Tree BC 2h/400°C showed the highest phosphorus adsorption capacity of 0.56 mg/g. Al-modified Orange Tree BC 3h/500°C showed the best performance for ammonia removal with an adsorption capacity of 1.72 mg/g. FTIR characterization showed that P = O bonds were formed after the adsorption of phosphorus by modified BC, N-H bonds were formed after ammonia adsorption. XPS analysis revealed that the key process of ammonia adsorption was the ion exchange between K⁺ and NH₄⁺. Phosphorus adsorption was related to oxidation and interaction between PO₄^3– and Fe³⁺. According to XRD results, ammonia was found in the form of potassium amide, while phosphorus was found in the form of iron hydrogen phosphates. The sorption isotherms showed that the Freundlich equation fits better for phosphorus adsorption, while the Langmuir equation fits better for ammonia adsorption. The simulated runoff infiltration experiment showed that 97.3% of ammonia was removed by Al-modified Orange tree BC 3h/500°C, and 92.9% of phosphorus was removed by Fe-modified Tea tree BC 2h/400°C.     

Resource utilization of typical biomass wastes as biochars in removing plasticizer diethyl phthalate from water: characterization and adsorption mechanisms

● Six largely produced agricultural biomass wastes were pyrolyzed into biochars. ● Feedstock type significantly determined physiochemical properties of biochars. ● The biochars showed powerful adsorption capabilities to Plasticizer DEP. ● Giant reed biochar with higher DEP adsorption was a prominent sorbent. Plastic pollution as a global environmental issue has become a research hotspot, among which the removal of inherent plasticizer (e.g., phthalic acid esters, PAEs) received increasing attention. However, the effects of biochars derived from different feedstocks on the adsorption of PAEs are poorly understood. Thus, the characteristics of biochars derived from six largely produced biomass wastes in China at 400 °C, as well as their performance in adsorption of diethyl phthalate (DEP), one of frequently detected PAEs in aqueous environment, were investigated. The results indicated that the variation in feedstock type showed significant changes in the properties (e.g., porosity, specific surface area, surface functional groups) of biochars, which affected DEP adsorption and desorption. Pseudo-second order and Freundlich models fitted the adsorption data well, and adsorption mechanisms mainly included hydrophobic effect, followed by micropore filling, hydrogen bonding, and π-π EDA interactions. Adsorption thermodynamics revealed that the adsorption was a spontaneous and exothermic the adsorption capacities of DEP on these biochars slightly decreased with the increasing pH but increased with the increasing ionic strength. Among these biochars, the giant reed biochar with relatively higher DEP adsorption and low desorption exhibited the great efficiency for DEP removal as an environment-friendly sorbent. These results highlighted the significant roles of micropore filling and hydrogen bond in determining adsorption capacity of designed biochars prepared from selecting suitable agricultural straws and wetland plant waste to typical plasticizer. The findings are useful for producing designed biochars from different biomass wastes for plasticizer pollution control.     

不同作物原料热裂解生物质炭对溶液中Cd2+和Pb2+的吸附特性

选择由小麦秸秆、玉米秸秆和花生壳经350~500℃热裂解制成的生物质炭,研究生物黑炭对水溶液中Cd2+和Pb2+的吸附特性,分析了pH值、吸附时间、溶液初始质量浓度、生物质炭粒径和投加量对吸附效果的影响。结果表明:生物质炭对Cd2+和Pb2+的吸附约10 min即达平衡;3种生物质炭对Cd2+和Pb2+的等温吸附均可用Langmuir方程和Freundlich方程拟合,玉米秸秆炭对Cd2+和Pb2+的最大吸附量远大于小麦秸秆炭和花生壳炭;在生物黑炭投加量为150 mg(6 g.L-1)时,3种生物黑炭对溶液Cd2+的去除率均在90%以上,玉米秸秆炭对溶液Pb2+的去除率达90.30%,而小麦秸秆炭和花生壳炭的去除率仅为52%和47%,玉米秸秆炭有望成为处理重金属污染废水的新型吸附材料。     

Biochars derived from carp residues: characteristics and copper immobilization performance in water environments

● P-rich carp residues-derived biochars presented excellent Cu sorption capacity. ● Sorption mechanisms of Cu on CRBs were mainly precipitation and surface complexation. ● CRBs could immobilize Cu and reduce its bioavailability in aquatic environment. Heavy metal pollution has attracted worldwide attention because of its adverse impact on the aquatic environment and human health. The production of biochar from biowaste has become a promising strategy for managing animal carcasses and remediating heavy metal pollution in the aquatic environment. However, the sorption and remediation performance of carp residue-derived biochar (CRB) in Cu-polluted water is poorly understood. Herein, batches of CRB were prepared from carp residues at 450–650 °C (CRB450–650) to investigate their physicochemical characteristics and performance in the sorption and remediation of Cu-polluted water. Compared with a relatively low-temperature CRB (e.g., CRB450), the high-temperature biochar (CRB650) possessed a large surface area and thermodynamic stability. CRB650 contained higher oxygen-containing functional groups and P-associated minerals, such as hydroxyapatite. As the pyrolytic temperature increased from 450 to 650°C, the maximum sorption capacity of the CRBs increased from 26.5 to 62.5 mg/g. The adsorption process was a type of monolayer adsorption onto homogenous materials, and the sorption of Cu²⁺ on the CRB was mainly based on chemical adsorption. The most effective potential adsorption mechanisms were in order of electrostatic attraction and cation-π interaction > surface complexation and precipitation > pore-filling and cation exchange. Accordingly, the CRBs efficiently immobilized Cu²⁺ and reduced its bioavailability in water. These results provide a promising strategy to remediate heavy metal-polluted water using designer biochars derived from biowastes, particularly animal carcasses.     

不同作物原料热裂解生物质炭对溶液中Cd2＋和Pb2＋的吸附特性

选择由小麦秸秆、玉米秸秆和花生壳经350-500℃热裂解制成的生物质炭,研究生物黑炭对水溶液中Cd2＋和Pb2＋的吸附特性,分析了pH值、吸附时间、溶液初始质量浓度、生物质炭粒径和投加量对吸附效果的影响。结果表明：生物质炭对Cd2＋和Pb2＋的吸附约10 min即达平衡;3种生物质炭对Cd2＋和Pb2＋的等温吸附均可用Langmuir方程和Freundlich方程拟合,玉米秸秆炭对Cd2＋和Pb2＋的最大吸附量远大于小麦秸秆炭和花生壳炭;在生物黑炭投加量为150 mg（6 g.L-1）时,3种生物黑炭对溶液Cd2＋的去除率均在90%以上,玉米秸秆炭对溶液Pb2＋的去除率达90.30%,而小麦秸秆炭和花生壳炭的去除率仅为52%和47%,玉米秸秆炭有望成为处理重金属污染废水的新型吸附材料。     

Metal immobilization by sludge-derived biochar: roles of mineral oxides and carbonized organic compartment

Pyrolyzing sludge into biochar is a potentially promising recycling/disposal solution for municipal wastewater sludge, and the sludge-derived biochar (SDBC) presents an excellent sorbent for metal immobilization. As SDBC is composed of both mineral oxides and carbonized organic compartment, this study therefore compared the sorption behaviour of Pb and Zn on SDBC to those of individual and mixture of activated carbon (AC) and amorphous aluminium oxide (Al₂O₃). Batch experiments were conducted at 25 and 45 °C, and the metal-loaded sorbents were artificially aged in the atmosphere for 1–60 days followed by additional sorption experiments. The Pb sorption was generally higher than Zn sorption, and the co-presence of Pb reduced Zn sorption on each studied sorbent. Higher sorption capacities were observed at 45 °C than 25 °C for SDBC and AC, while the opposite was shown for Al₂O₃, indicating the significance of temperature-dependent diffusion processes in SDBC and AC. Nevertheless, metal sorption was more selective on Al₂O₃ that showed a greater affinity towards Pb over Zn under competition, correlating with the reducible fraction of sequential extraction. Furthermore, significant amounts of Pb and Zn were additionally sorbed on SDBC following 30-day ageing. The X-ray diffraction revealed the formation of metal-phosphate precipitates, while the X-ray photoelectron spectroscopy showed a larger quantity of metal–oxygen bonding after 30-day ageing of metal-loaded SDBC. The results may imply favourable long-term transformation and additional sorption capacity of SDBC. In conclusion, SDBC resembles the sorption characteristics of both organic and mineral sorbents in different aspects, presenting an appropriate material for metal immobilization during soil amendment.     

土壤和沉积物中有机质对双酚A和17α-乙炔基雌二醇的吸附行为

研究了土壤和沉积物原始样品bulk及其有机质组分(非水解性有机质NHC、碳黑BC和腐殖酸HA)对17α-乙炔基雌二醇(EE2)和双酚A(BPA)的吸附行为.所有的吸附等温线都很好地拟合了Freundlich模型,除HA和bulk外,所有的吸附等温线都为显著的非线性(n值为0.46—0.76).对于EE2和BPA的吸附非线性因子n值都存在这样的关系:HA>NHC>BC.EE2以有机碳归一化的Freundlich吸附能力(lgKOC)有BC>NHC>bulk>HA的关系,说明有机质成熟度越高,对EE2或者BPA的吸附能力越高.在土壤和沉积物有机质SOM(NHC、BC和HA)对吸附BPA和EE2的贡献上,NHC、BC和HA对沉积物和土壤对BPA总吸附贡献上要明显弱于它们对EE2的贡献.除了内分泌干扰物(EDCs)的疏水性影响EE2和BPA的吸附能力的差异外,分子大小和带电子苯环数也影响它们的吸附能力差异.     

Sorption of aromatic organophosphate flame retardants on thermally and hydrothermally produced biochars

• TPhP showed faster and higher sorption on biochars than TPPO. • Pyrochars had higher sorption capacity for TPPO than hydrochar. • Hydrophobic interactions dominated TPhP sorption by biochars. • The π-π EDA and electrostatic interactions are involved in sorption. Aromatic organophosphate flame retardant (OPFR) pollutants and biochars are commonly present and continually released into soils due to their increasingly wide applications. In this study, for the first time, the sorption of OPFRs on biochars was investigated. Although triphenyl phosphate (TPhP) and triphenylphosphine oxide (TPPO) have similar molecular structures and sizes, TPhP exhibited much faster and higher sorption than TPPO due to its stronger hydrophobicity, suggesting the dominant role of hydrophobic interactions in TPhP sorption. The π-π electron donor–acceptor (EDA) interactions also contributed to the sorption process, as suggested by the negative correlation between the sorption capacity of the aromatic OPFRs and the aromatic index (H/C atomic ratios) of biochar. Density functional theory calculations further showed that one benzene ring of aromatic OPFRs has no electrons, which may interact with biochar via π-π EDA interactions. The electrostatic attraction between the protonated P = O in OPFRs and the negatively charged biochar was found to occur at pH below 7. This work provides insights into the sorption behaviors and mechanisms of aromatic OPFRs by biochars.