纳米零价铁改性生物炭对水中氨氮的吸附特性及机制

传统生物炭材料对水中氨氮(NH⁺₄-N)的吸附效果不佳.以生物炭为载体负载纳米零价铁制得生物炭基纳米零价铁复合吸附剂nZVI@BC,通过吸附实验,考察nZVI@BC对NH⁺₄-N的吸附特性,并采用SEM-EDS、 BET、 XRD和FTIR分析nZVI@BC的组成和结构特性,探讨nZVI@BC吸附NH⁺₄-N的主要机制.结果表明,在298K下铁/生物炭质量比为1∶30时制备的复合吸附剂(nZVI@BC1/30)对NH⁺₄-N的吸附性能最佳,比负载前生物炭的吸附量提高了45.96%,饱和吸附量可达16.60 mg·g^-1.伪二级动力学模型和Langmuir模型更符合nZVI@BC1/30对NH⁺₄-N的吸附过程.共存阳离子与NH⁺₄-N之间存在竞争吸附,其对nZVI@BC1/30吸附NH⁺     

裂解温度对新疆棉秆生物炭物理化学性质的影响

生物质的裂解温度影响其所生产的生物炭炭的物理和化学性质,进而影响其田间应用效果。棉花秸秆是干旱区特别是新疆地区的主要农业生物质资源,其生物炭利用途径有望克服现有秸秆利用途径的不足,但对棉秆生物炭理化性质及其变化的认识还很缺乏。本文在不同的裂解温度下对新疆棉秆生物炭物理和化学性质进行研究,发现随着裂解温度的升高,生物炭的产率、阳离子交换量、O/C和H/C值降低,p H、电导和持水性能提高,Na+、K+趋势不明显,Cl-和SO2-4等盐碱化离子以及Ca~(2+)、Mg~(2+)营养元素含量随温度的升高降低;C、N、S、C/N和灰分等均提高,NH+4-N在550℃碳化条件下含量最高。因此在田间应用中,应针对土壤特点和解决的问题,调控碳化温度,从而达到趋利避害的目的。     

两性修饰磁化炭对紫色土吸附菲的增强作用

为了验证两性修饰磁化炭材料对紫色土吸附菲的增强作用,采用共沉淀负载Fe_3O_4法和湿法有机负载分别制备了磁化炭(MC)和不同十二烷基二甲基甜菜碱(BS-12)修饰比例的两性修饰磁化炭(BS+MC),将其以1%的质量比加入到紫色土(PS)中,分别形成PS_(MC)和PS_(BS+MC)混合样品,批处理法研究各混合样品对菲的等温吸附和热力学特征,并对比了不同温度、离子强度和pH值对菲吸附的影响。结果表明:(1) MC和BS-MC材料的添加均增强了PS对菲的吸附能力,菲吸附量呈现PS_(200BS+MC)> PS_(150BS+MC)> PS_(100BS+MC)> PS_C> PS_(MC)> PS_(50BS+MC)> PS_(25BS+MC)> PS的趋势,PS_(BS+MC)对菲的吸附量随着添加材料上BS-12修饰比例的增加而增加。(2)菲在各供试土样上的吸附均表现为增温负效应(物理吸附),溶液pH值变化仅对PS_(150BS+MC)和PS_(200BS+MC)吸附菲有显著影响。离子强度增大不利于各供试土样对菲的吸附。(3) Henry模型适用于描述菲在供试土样上的等温吸附,且该过程呈现自发的、焓减和熵增的特征。从PS_C到PS_(MC)再到PS_(BS+MC),吸附过程呈现自发性、放热量和混乱度均增大的特征。     

土壤矿物质-可溶态生物炭的交互作用及其对碳稳定性的影响

将生物质转化为生物炭并输入土壤被认为是一种很有前景的碳封存技术.生物炭颗粒在土壤中会不断释放出可溶态生物炭,这部分生物炭不稳定,易被微生物分解.探明土壤组分矿物质对可溶态生物炭稳定性的影响对评估生物炭的碳封存作用具有重要意义.因此,本文以核桃壳生物炭为研究对象,通过批次吸附实验及微生物降解实验研究了2种代表性土壤矿物质高岭土和针铁矿与核桃壳生物炭可溶有机组分的结合机理,以及这种结合作用对可溶态生物炭稳定性的影响.结果表明:低浓度(如20 mg·L-1)可溶态生物炭条件下,高岭土与可溶态生物炭之间以Ca2+架桥作用为主,约占吸附总量的65%;高浓度(如80 mg·L-1)条件下,以范德华力为主,约占吸附总量的76%.随着可溶态生物炭初始浓度的升高,针铁矿对其吸附量先升高后下降,且以范德华力为主,Ca2+会抑制针铁矿对可溶态生物炭的吸附.被矿物质吸附后的可溶态生物炭,其微生物降解性显著下降,可降解的碳下降了47.9%~85.3%,土壤矿物质能够吸附保护可溶态生物炭,提高其在土壤中的稳定性.     

Enhanced photocatalytic activity of fish scale loaded TiO2 composites under solar light irradiation

Fish scale (FS) loaded TiO₂ composites were investigated as photocatalysts in degradation of Methyl Orange under solar light irradiation. Composites were prepared through sol-gel method by varying mass ratio of TiO₂/FS at 90:10, 70:30 and 50:50, respectively. The catalysts prepared in this study were characterized by using XRD, SEM, FT-IR and nitrogen sorption. The effects of solar irradiation, mass ratio of TiO₂/FS composites, irradiation time and catalyst loadings were studied. Synergistic effect was found in TiO₂/FS of 90:10 composite which performed higher photocatalytic degradation than synthesized TiO₂ under solar light irradiation. However, further increasing fish scale content in the composites reduced the photocatalytic activity drastically. Under solar light irradiation, all the catalysts in this study exhibited photocatalytic activity, except TiO₂/FS of 50:50 composite that only acted as a weak biosorbent without performing any photocatalytic property. Photocatalytic degradation increased with increasing catalyst loading and irradiation time but decreased with increased of initial dye concentration.     

CuFeO2改性生物炭对四环素的吸附特性

利用共沉淀和水热法于生物炭（BC250、BC350、BC450、BC550和BC650）负载CuFeO₂,得到的复合材料对水中四环素（TC）具有较好的去除效果.CuFeO₂与BC450质量比为2 ：1的CuFeO₂改性生物炭（CuFeO₂/BC450=2 ：1）对TC的吸附性能最强.TC于CuFeO₂/BC450=2 ：1的吸附符合颗粒内扩散模型,表明吸附是界面和孔隙扩散控制的过程.在中性pH、298 K下,CuFeO₂/BC450=2 ：1对TC的Langmuir最大吸附量为82.8 mg ·g^-1,远大于BC450的13.7 mg ·g^-1和CuFeO₂的14.8 mg ·g^-1.热力学结果表明,CuFeO₂/BC450=2 ：1对TC的吸附是自发和吸热过程.随pH增加,CuFeO₂/BC450=2 ：1对TC的吸附去除呈先增加后降低的趋势,中性条件时效果最佳.CuFeO₂/BC450=2 ：1对TC的强吸附得益于CuFeO₂负载对材料孔隙结构的改善、比表面积的增大和表面官能团、电荷属性的改变.研究结果为净化抗生素污染提供了一种高效的磁性吸附剂.     

Sorption of tetracycline to sediments and soils: assessing the roles of pH, the presence of cadmium and properties of sediments and soils

Batch sorption experiments were conducted to evaluate the sorption behavior of tetracycline (TC, H₃L) on sediments and soils in the presence and absence of cadmium (Cd), as affected by pH and properties of sediments and soils. The results indicated stronger nonlinearity and higher capacity of TC sorption on sediments than on soils. Sorption of TC also strongly depended on environmental factors and sediment/soil properties. Lower pH facilitated TC sorption through a cation exchange mechanism, which also took place at pH values above 5.5, where TC existed as a zwitterion (H₂L⁰) or anions (HL⁻ and L²⁻). When pH was above 7, however, ligand-promoted dissolution of TC might occur due to TC weakening the Al-O bond of aluminum oxide and the Fe-O bond of iron oxide. Natural organic matter (NOM) plays a more important role in TC sorption than cation exchange capacity (CEC) and clay contents. The presence of Cd (II) increased TC sorption on both sediments and soils, which resulted from the decrease of equilibrium solution pH caused by Cd²⁺ exchange with H⁺ ions of sediment/soil surfaces. The increase of TC sorption was also related to the formation of TC-Cd complexes, where Cd²⁺ acted as a bridge between the sediment/soil and TC.     

生物炭对黄绵土中NO3--N运移过程影响及模拟

为探究不同施加量生物炭对黄绵土NO₃^--N运移过程及特征的影响,以生物炭与黄绵土质量比分别为0%（T0）、1%（T1）、2%（T2）、3%（T3）、4%（T4）和5%（T5）的6组混合土样为研究对象,以NO₃^--N为示踪物质,通过室内土柱溶质运移模拟试验,研究了不同生物炭施加量对黄绵土中NO₃^--N运移过程影响并进行模型模拟.结果表明,NO₃^--N在黄绵土中的穿透曲线随生物炭施加量增加明显右移,峰值逐渐降低.初始穿透时间、完全穿透时间及穿透总历时均随生物炭施加量增大而增加,T1、T2、T3、T4和T5处理NO₃^-穿透总历时分别是T0的1.26、2.31、2.72、3.22和3.57倍.两区模型（TRM）的R²>0.997,RMSE<2.083,相较于对流-弥散方程（CDE）,TRM模型拟合精度更高,能较好地模拟不同含量生物炭施加后的黄绵土中NO₃^--N运移过程.对TRM模型拟合参数进行分析发现,随生物炭施加量增加,平均孔隙流速、水动力弥散系数和可动区含水比率均逐渐减小,而弥散度和质量交换系数呈现增加的趋势.研究显示,生物炭有效增强了黄绵土对NO₃^--N的固持能力,减少了NO₃^--N向地下水体的渗漏,对保持土壤肥力与防止地下水污染具有重要作用.     

生物质炭施用对土壤中氯虫苯甲酰胺吸附及消解行为的影响

分别在黑土、黄壤、红壤、紫色土和潮土中添加0.5%(质量分数)生物质炭,采用批处理等温吸附实验及室内消解实验测定了CAP的吸附等温线及消解动态,目的是揭示不同类型土壤中施用生物质炭对残留CAP的环境行为影响规律,为评估生物质炭田间施用综合生态效应,评价土壤残留CAP的环境污染风险提供理论依据.结果表明,生物质炭施用可提高土壤对CAP的吸附活性,但提高程度因土壤性质不同而异.有机质含量较高的黑土中添加生物质炭,吸附农药Kd值提高了2.17%,而有机质含量较低的潮土添加等量生物质炭后则提高了139.13%.生物质炭施入土壤后其对农药吸附活性受到不同程度抑制.与施入土壤前比较,生物质炭施入黑土、黄壤、红壤、紫色土和潮土中后吸附常数KF,biochar分别降低了96.94%、90.6%、91.31%、68.26%和34.59%.CAP在黑土、黄壤、红壤、紫色土和潮土中的消解半衰期为115.52、133.30、154.03、144.41和169.06 d,而在添加生物质炭的土壤中消解半衰期分别延长了20.39、35.76、38.51、79.19和119.75 d.与吸附实验结果一致,生物质炭施入黑土对延缓农药土壤消解作用最小,而潮土中施入生物质炭效果最明显.本研究表明生物质炭施入土壤后可增强对农药的吸附作用,延缓农药的土壤消解,但影响程度与土壤性质有关.     

Enhanced removal of Cr(VI) by biochar with Fe as electron shuttles

Biochar is extensively used as an effective soil amendment for environmental remediation. In addition to its strong contaminant sorption capability, biochar also plays an important role in chemical transformation of contaminant due to its inherent redox-active moieties. However, the transformation efficiency of inorganic contaminants is generally very limited when the direct adsorption of contaminants on biochar is inefficient. The present study demonstrates the role of Fe ion as an electron shuttle to enhance Cr(VI) reduction by biochars. Batch experiments were conducted to examine the effects of Fe(III) levels, pyrolysis temperature of biochar, initial solution pH, and biochar dosage on the efficiency of Cr(VI) removal. Results showed a significant enhancement in Cr(VI) reduction with an increase in Fe(III) concentration and a decrease of initial pH. Biochar produced at higher pyrolysis temperatures (e.g., 700°C) favored Cr(VI) removal, especially in the presence of Fe(III), while a higher biochar dosage proved unfavorable likely due to the agglomeration or precipitation of biochar. Speciation analysis of Fe and Cr elements on the surface of biochar and in the solution further confirmed the role of Fe ion as an electron shuttle between biochar and Cr(VI). The present findings provide a potential strategy for the advanced treatment of Cr(VI) at low concentrations as well as an insight into the environmental fate of Cr(VI) and other micro-pollutants in soil or aqueous compartments containing Fe and natural or engineered carbonaceous materials.     

Simultaneous adsorption of As(Ⅲ) and Pb(Ⅱ) by the iron-sulfur codoped biochar composite:Competitive and synergistic effects

Simultaneous elimination of As(Ⅲ) and Pb(Ⅱ) from wastewater is still a great challenge.In this work,an iron-sulfur codoped biochar (Fe/S-BC) was successfully fabricated in a simplified way and was applied to the remediate the co-pollution of As(Ⅲ) and Pb(Ⅱ).The positive enthalpy indicated that the adsorption in As-Pb co-pollution was an endothermic reaction.The mechanism of As(Ⅲ) removal could be illustrated by surface complexation,oxidation and precipitation.In addition to precipitation and com...     

负载AsOB离子交换纤维FFA-1去除水中三价砷

对比两组填充了离子交换纤维FFA-1的固定床反应器（R1和R2）的运行处理效果,研究负载功能微生物的离子纤维组合工艺对不同浓度As（III）的去除能力.研究结果表明接种了三价砷氧化菌（AsOB）的R1能够长期稳定并高效地去除不同浓度（1~10 mg·L^-1）As（III）.未接种AsOB的R2反应器初期无法去除As（III）,随着微生物逐步侵入R2反应器,7 d后R2反应器As（III）去除率逐渐与R1接近.相对于一直稳定运行的R1反应器,每次提升进水中As（III）浓度后R2去除率呈现先下降后上升的趋势.同时,在运行过程中发现进水中NO₃^-和SO₄^2-等阴离子也会被R1和R2去除从而导致As（III）去除总量的下降.离子交换纤维FFA-1再生实验证实R1和R2中的纤维与原始的离子交换纤维FFA-1再生效果相当（再生率均达到90%以上）.进一步研究微生物种群结构在反应器中的变化发现离子交换纤维作为微生物载体可能是影响微生物种群结构的重要因素.本研究证实了功能微生物AsOB联合离子交换纤维可以作为一种高效去除地下水中三价砷的工艺,具有很好的应用前景.     

木屑生物炭对填料土的氮磷吸附及雨水持留改良影响

现阶段生物滞留系统的填料土存在氮磷营养盐净化效果不稳定、雨水持留能力下降等问题.为评估木屑生物炭作为生物滞留系统填料土添加剂的改良效果,选用对照填料土和施用了木屑生物炭的改良填料土进行对比研究,通过理化性质测试、等温吸附实验、土柱实验和土水特征曲线测定,研究木屑生物炭对填料土的改良影响与优化机制.结果表明,木屑生物炭孔隙率大、比表面积大、饱和含水率高和CEC高,可优化填料土的结构,提升填料土的离子交换能力;木屑生物炭对填料土的氮磷吸附改良效果突出,对NH4+-N的最大吸附量提高了 2.80倍,去除率由31.30％提高至64.10％,对PO43--P的最大吸附量提高了 1.28倍,去除率由61.90％提高至90.00％;经木屑生物炭改良后,填料土的饱和含水率提高1.63倍,渗透系数提高2.43倍,在各含水率下的基质吸力明显增加.木屑生物炭的添加可优化生物滞留系统填料土的性能,加强对雨水径流中氮磷营养盐的吸附,提高系统的渗透性和雨水持留能力.     

29种湿地填料对氨氮的吸附解吸性能比较

为筛选出性能更好的人工湿地填料,采用等温吸附-解吸试验,测定了29种天然和非天然人工湿地填料的孔隙率、渗透系数及其对NH₃-N的吸附-解吸特性. 结果表明:锯末、瓷砖、鸡蛋壳、瓷砂陶粒、火山岩等材料的孔隙率较大,瓷砂陶粒、海绵铁、石灰石、页岩陶粒、砾石等材料的渗透系数较大;Freundlich和Langmuir等温吸附方程能较好地拟合各填料对NH₃-N的吸附特征,通过Langmuir等温吸附方程计算,对NH₃-N的理论饱和吸附量居前5位的填料依次是火山岩(1.700 0 mg/g)、瓷砂陶粒(1.620 0 mg/g)、生物炭(1.353 0 mg/g)、沸石(1.350 0 mg/g)、石榴石(1.190 0 mg/g). 吸附速率的变化与填料吸附NH₃-N的途径密切相关. 吸附饱和的生物炭、焦炭、大理黏土、沸石、磁铁矿、石英砂主要通过离子交换作用吸附NH₃-N,稳定性好,解吸率均小于20%;瓷砂陶粒和火山岩对NH₃-N的解吸率分别为24.50%和35.51%,既有物理吸附也有离子交换作用. 火山岩、瓷砂陶粒、生物炭、沸石对较高浓度NH₃-N的吸附效果较好. 研究显示,火山岩、生物炭、瓷砂陶粒、沸石等适合作为人工湿地中吸附NH₃-N的填料.      

改性污泥基生物炭的性质与重金属吸附效果

为提高污泥基生物炭在高钙溶液体系中对重金属阳离子的吸附能力,将Fe₂O₃、MnO₂、ZnO与市政污泥以质量比1 ∶10（以过渡金属元素质量计）混合共热解,制备改性生物炭;表征改性生物炭的组成、官能团分布和表面性质,考察其对典型重金属阳离子Cd²⁺的吸附效果.过渡金属氧化物可促进污泥的热解,改性生物炭的H/C原子比均低于0.31,碳链裂解脱氢更彻底.改性生物炭中Fe、Mn保留较好,分别主要以单质和氧化物形态存在;而Zn流失较多.改性生物炭中的孔隙以介孔为主,平均孔径约3.8 nm,比表面积在50 m²·g^-1以上.初始浓度约200 mg·L^-1的Cd²⁺溶液中,Ca²⁺初始浓度从0 mg·L^-1升高到约200 mg·L^-1,Fe改性生物炭对Cd²⁺的吸附容量从43.17 mg·g^-1降至27.88 mg·g^-1,但仍较未改性生物炭高10 mg·g^-1以上,在含钙溶液体系中表现出了对Cd²⁺更强的吸附性能.Fe₂O₃较MnO₂和ZnO对市政污泥基生物炭吸附重金属的强化效果更好.     

生物炭添加和灌溉对温室番茄地土壤反硝化损失的影响

生物炭添加和灌溉是番茄地常用的田间管理措施,然而其对反硝化的影响还不清楚.本研究种植试验设置3个灌溉量水平分别为估算作物生育期需水量ET0的50%(W50%)、75%(W75%)、100%(W100%)和3个生物炭添加水平分别为B0(折合纯碳,0)、B25(折合纯碳,25 t·hm-2)、B50(折合纯碳,50 t·hm-2),在2014年和2015年番茄收获后,每个试验小区采集具有代表性的土样进行室内培养试验,采用乙炔抑制法来研究土壤的反硝化损失和不加乙炔研究N_2O的排放量.结果表明生物炭和灌溉量显著改变了土壤的理化性质.与B0相比,添加生物炭能够提高土壤全碳、全氮含量和pH值,降低铵态氮、硝态氮含量,而灌水量降低了土壤中全氮和全碳的含量.因此,与B0/W50%相比,B25/W75%和B50/W100%处理显著减少了反硝化损失量(P0.05).生物炭和灌溉量的交互作用对土壤无机氮含量和反硝化损失的影响均达到显著水平(P0.05),且对硝态氮的影响表现为灌溉量生物炭添加量两者交互作用,对铵态氮的影响表现为生物炭添加量灌溉量两者交互作用,对反硝化损失的影响表现为灌溉量生物炭添加量两者交互作用.反硝化损失量与土壤中无机氮含量、(CO_2-C)矿化量与N_2O排放量均呈正相关关系.不同生物炭添加量和灌溉量处理后明显影响了N_2O/DN(P0.05),培养结束时,各处理下的N_2O累积排放量/DN累积排放量差异较大,介于0.31%~1.88%.     

微波改性MWNTs/TiO2复合材料对1,2,3-三氯苯的光催化降解研究

在微波辐照干化的条件下用溶胶-凝胶法制备了MWNTs/TiO2复合光催化剂.对该复合材料的表征表明：随着微波功率逐渐增大至400 W,MWNTs/TiO2复合材料管径逐渐变小,且在400 W时制备的MWNTs/TiO2复合材料分散性较好.进一步增大微波功率导致复合材料的管径增大,分散性降低.研究了不同微波辐照条件下制备的MWNTs/TiO2复合光催化剂对1,2,3-三氯苯的光催化降解效果,结果表明,该复合光催化剂对1,2,3-三氯苯的光降解遵循一级反应动力学;在微波功率为400 W、辐照时间为5 min情况下制备的复合光催化剂对1,2,3-三氯苯的降解速率最快,其反应常数为0.023 7 min^-1,该值比非微波加热干化的同样复合材料的反应速率常数值提高了52%.     

阴离子表面活性剂改性水滑石吸附硝基苯的特性研究

以阴离子表面活性剂十二烷基硫酸钠(sodium dodecyl sulfate,SDS)为改性剂,采用共沉淀法在不同表面活性剂浓度,0.5～2.0理论阴离子交换容量(theoretical anion exchange capacity,TAEC)条件下制备了有机水滑石LDH-DS,并用XRD、FT-IR表征了样品的结构特征.结果表明十二烷基硫酸根成功插层进入LDH层间,d003底面间距由0.80 nm增大至3.98 nm.同时研究了LDH-DS对硝基苯的吸附性能,表明有机水滑石对硝基苯的等温吸附曲线符合线型方程(R2>0.99),吸附过程主要为分配作用.随着样品中SDS负载量的增加,LDH-DS对硝基苯的吸附系数Kd相应增强,但有机碳标化的吸附系数Koc值基本保持恒定.吸附热力学实验显示吸附过程为吸热反应,熵增大是吸附过程的驱动力.     

Removal of cobalt(Ⅱ) ion from aqueous solution by chitosan-montmorillonite

Montmorillonite （MMT） modified with chitosan （CTS, molecular weight = S x 104） was applied to remove heavy metal cations by using Co2＋ as a model ion. An increase in MMT interlayer distance observed from X-ray diffraction indicates the intercalation of CTS into MMT. Together with the results of scanning electron microscopy and Fourier transform infrared spectroscopy, it was concluded that the composite material of CTS and MMT （CTS-- MMT） was prepared successfully. The mass ratio of CTS to MMT had a strong influence on the adsorption performance of CTS-MMT. The highest adsorption value of 150 mg/g was obtained over the composite material with CTS to MMT mass ratio of 0.25, which is much higher than those reported in other studies. The adsorption isotherms and kinetic results indicated that Co2＋ was adsorbed over CTS-MMT in a multilayer model, and the chemical sorption of Co2＋ was determined to be the rate-limiting step.     

Removal of Cs from water and soil by ammonium-pillared montmorillonite/Fe3O4 composite

To remove cesium ions from water and soil, a novel adsorbent was synthesized by following a one-step co-precipitation method and using non-toxic raw materials. By combining ammonium-pillared montmorillonite (MMT) and magnetic nanoparticles (Fe₃O₄), an MMT/Fe₃O₄ composite was prepared and characterized. The adsorbent exhibited high selectivity of Cs⁺ and could be rapidly separated from the mixed solution under an external magnetic field. Above all, the adsorbent had high removal efficiency in cesium-contaminated samples (water and soil) and also showed good recycling performance, indicating that the MMT/Fe₃O₄ composite could be widely applied to the remediation of cesium-contaminated environments. It was observed that the pH, solid/liquid ratio and initial concentration affected adsorption capacity. In the presence of coexisting ions, the adsorption capacity decreased in the order of Ca^2 + > Mg^2 + > K⁺ > Na⁺, which is consistent with our theoretical prediction. The adsorption behavior of this new adsorbent could be expressed by the pseudo-second-order model and Freundlich isotherm. In addition, the adsorption mechanism of Cs⁺ was NH₄⁺ ion exchange and surface hydroxyl group coordination, with the former being more predominant.