水稻秸秆生物碳的结构特征及其对有机污染物的吸附性能

以水稻秸秆为原料,采用限氧裂解法制备了不同温度(100 ～ 700℃)的秸秆生物碳,用TG-DTG热重分析、CHNO元素分析、FTIR、BET-N2比表面及孔径分布等手段表征生物碳的组成与结构,研究生物碳吸附水中硝基苯、对硝基甲苯、萘、菲等有机污染物的性能及影响因素,探讨其作用机制及构-效关系,试图为高效利用废弃农业秸秆资源、制备廉价的有机物吸附材料提供理论依据.结果表明,水稻秸秆生物碳含有丰富的有机碳组分和无机矿物组分,随着裂解温度升高,生物碳中有机组分的含碳量逐渐升高、极性减弱、芳香性增强,而无机矿物组分的相对含量则不断增加;当裂解温度从300℃升至400℃时,比表面积突然增大(0.16→110 m2·g-1)、微孔结构被打开,主要由于水稻秸秆中纤维素组分大量分解所致.水稻秸秆生物碳吸附有机污染物的主要介质为有机组分,等温吸附曲线符合Freundlich方程,回归参数N、logKf与生物碳的芳香性指数(H/C原子比)呈良好的线性关系;定量描述了分配作用和表面吸附作用的相对贡献.随碳化温度升高,等温吸附曲线由线性变为非线性,吸附机制从分配作用→分配作用+表面吸附作用→表面吸附作用;分配作用部分与有机污染物的logKow呈正相关,而表面吸附则与污染物的疏水性、分子尺寸及其与生物碳的极性匹配性有关.     

互花米草生物炭的添加对土壤吸附三氯生的影响及其机制研究

互花米草作为入侵物种,在我国沿海分布广泛,对沿海生态造成负面影响.本研究以互花米草资源化利用为出发点,在300℃和600℃下将其热解分别制得BC300和BC600两种生物炭,采用批量平衡法研究了生物炭添加对土壤吸附三氯生(TCS)的影响及其机制.结果表明,BC300内含有未炭化有机质,对TCS的吸附以分配作用为主,有利于对高浓度TCS的吸附;BC600有较大的比表面积,对TCS的吸附以表面吸附为主,有利于对低浓度TCS的吸附.生物炭添加能够促进土壤对TCS的吸附,且吸附量随生物炭添加比例的增加而增加;添加BC300的土壤对TCS的吸附量要显著高于添加BC600的土壤,这主要与生物炭的结构特征及其对土壤p H值的影响有关.因此,添加300℃下制备的互花米草生物炭可以有效地降低土壤中TCS的环境风险,同时也能为护花米草的资源化利用提供一条可行途径.     

老化过程对生物质炭吸附-解吸附邻苯二甲酸二乙酯的影响

将稻草和竹锯末在500℃条件下炭化制备得到两种生物质炭,并与土壤充分混合老化处理30 d.通过批处理恒温振荡法,研究了老化过程(恒湿和干湿交替)、制备原材料、不同施用量(0、0.1%和0.5%,质量分数)和土壤类型(熟化红壤、新垦红壤)对生物质炭吸附邻苯二甲酸二乙酯(DEP)的影响.结果表明,土壤中添加生物质炭的处理对DEP的吸附能力显著增强,且随着生物质炭添加量的增加,各个处理对DEP的吸附能力增强.与稻草炭相比,竹炭对DEP具有更强的吸附能力并且更难以解吸附DEP.与添加新鲜生物质炭的土壤相比,老化过程降低了加炭处理对DEP的吸附能力.不同老化条件下,生物质炭吸附DEP能力的降低顺序也不同,主要表现为:干湿交替恒湿.     

Role of sorbent surface functionalities and microporosity in 2,2’,4,4’-tetrabromodiphenyl ether sorption onto biochars

The study provides insight into the combined effect of sorbent surface functionalities and microporosity on2,2 ′,4,4 ′-tetrabromodiphenyl ether (BDE-47) sorption onto biochars. A series of biochars prepared underdifferent conditionswere used to test their sorption behaviorswith BDE-47. The extents of sorption behaviorswere parameterized in terms of the single-point adsorption equilibrium constant (Koc ) at three equilibrium concentration (C e ) levels (0.001Sw (solubility), 0.005Sw , and 0.05Sw )whichwasdetermined using the Freundlich model. To elucidate the concentration-dependentdominant mechanisms for BDE-47 sorption onto biochars, K ocwas correlatedwith four major parameters using multiple parameter linear analysis accompaniedwith significance testing. The results indicated that at low concentration (Ce = 0.001Sw ), the surface microporosity term,which represented a pore-filling mechanism, contributed significantly to this relationship,while as concentrationwas increased to higher levels, surface functionality related to surface adsorption began to take thedominant role,whichwas further confirmed by the results of Polanyi-based modeling. Given the above results, adual mode model based on Dubinin-Radushkevich andde Boer-Zwikker equationswas adopted to quantitatively assess the changes of significance of surface adsorption aswell as that of pore fillingwith sorption processdevelopment. In addition, UV spectra of four typical aromatic compoundswhich represented the key structural fragments of biochars before and after interactionswith BDE-47were analyzed todetermine the active functional groups and supply complementary evidence for thedominant interaction force for surface adsorption, based onwhich π-π electron-donor-acceptor interactionwas proposed to contribute greatly to surface adsorption.     

生物炭对污泥施用土壤中三氯生生物有效性和微生物群落结构的影响

污泥农用是三氯生(TCS)进入土壤的一个主要途径,TCS进入土壤后会通过食物链危及人体健康.基于此,本实验将含有TCS的污泥施入土壤后,分别添加不同比例(1%、2%和5%)在300℃和600℃下制备的生物炭(BC300和BC600),进行了为期90 d种植黄瓜的盆栽实验,研究了生物炭对土壤中TCS生物有效性和微生物群落结构的影响.结果表明,生物炭的添加显著降低了黄瓜根系对TCS的富集(p0.05),且生物炭添加量越多,根系富集的TCS量越少.添加1%和2%BC600处理的黄瓜根系富集的TCS量都显著低于添加相应比例BC300处理的黄瓜根系富集量.只添加生物炭并不能显著降低土壤中TCS的含量,添加生物炭并种植黄瓜能够显著降低土壤中TCS含量(去除率为31.57%～50.31%),且生物炭添加量越多,土壤中TCS去除率越高,但相同添加量下BC300和BC600对土壤中TCS的去除无显著性差异(p0.05).添加不同比例的生物炭对土壤中微生物群落结构有明显的影响,特别是添加不同比例的BC600,但种植黄瓜能够降低生物炭对土壤微生物群落结构改变的影响.     

Numerical simulation of PAHs sorption/desorption on soil with the influence of Tween80

In this paper, the influences of inionic surfactant Tween80 on polycyclic aromatic hydrocarbons （PAHs） sorption/desorption on artificially contaminated soil were studied, and γ model was applied to simulate the influences. Results showed that, with the use of Tween 80, the sorption behaviors of PAHs on soil altered significantly. Adsorbed Tween 80 increased the sorption amount of PAHs while the dissolved Tween80 increased the apparent solubility of PAHs. These two processes exert influences on the sorption coefficient of PAHs in soil-water system, which can be depicted by apparent sorption coefficient. The partition coefficients （the soil/water partition coefficient of PAHs and surfactants obtained fxom sorption experiments） and statistical parameters used in the amended γ model were obtained in independent experiments. With these parameters, the γ model could provide a satisfactory independent prediction of PAHs release from soil to aqueous phase at two surfactant concentrations.     

非平衡吸附对核素迁移的影响及平衡速率参数的确定

放射性核素以水为载体在多孔介质中迁移时,吸附和解吸作用不容忽视吸附和解吸是一非平衡过程．非平衡状态下吸附和解吸达到平衡的快慢程度可以用平衡速率参数a来表征本文首次定量分析了非平衡吸附对核素迁移的影响,提出基于室内分配系数实验求取a值的方法,并将室内实验得出的a值同原位核素迁移试验拟合值进行比较;结果表明用此方法求出的a值可作为非平衡吸附核素迁移数学模型的主要参数依据。     

溶解性有机质对芘在土壤中吸附解吸的影响

从腐解不同阶段的水稻秸秆提取溶解性有机质(DOM),用DAX-8树脂分组的方法分析了其亲疏水性,并研究了提取到的DOM对芘在土壤中吸附-解吸行为的影响.结果表明,随秸秆腐解时间的延长,产生DOM中亲水性组分减少,疏水性组分增多.在本试验所研究的吸附解吸实验条件下,芘在土壤中的吸附解吸均可用线性方程进行描述.加入DOM后,芘的吸附受到显著抑制(p0.01),并且随腐解时间延长,抑制作用增强;芘在土壤中存在解吸迟滞现象,加入DOM后迟滞现象减弱,促进了芘在土壤中的解吸.随腐解作用的进行,DOM促进芘解吸的作用增强,解吸迟滞系数减小.这是由于随秸秆腐解作用的进行,产生DOM中疏水性组分含量增多,其对芘的增溶作用增强所致.     

Numerical modeling of radionuclide migration in porous media with nonequilibrium sorption

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农药在土壤－水环境中归宿的主要支配因素──吸附和脱附

综述了近年来农药在土壤－水环境中吸附－脱附研究的实验方法、影响因素、数学描述、作用机理等方面的工作。重点讨论了农药与土壤粘土矿物、有机物（腐殖酸、富菲酸等）的物理化学键合机理。     

生物炭增强黄绵土对西替利嗪的吸附作用

生物炭可以作为稳定剂控制污染物在土壤中的迁移转化,削减其环境风险.以西替利嗪(cetirizine,CTZ)为目标污染物,黄绵土为供试土壤,采用吸附批实验法,研究添加了不同质量比、不同碳化温度核桃壳生物炭的土壤对CTZ的吸附作用.结果表明,生物炭对CTZ的吸附能力均强于土壤.添加400~700℃制备的生物炭可显著增强黄绵土对CTZ的吸附能力,这主要与添加生物炭后比表面积(SA)和含碳量相比土壤增大有关.土壤-生物炭混合体系(除添加300℃制备的生物炭)对CTZ吸附分配系数的实验值相比理论值偏小.这是由于土壤和生物炭组分之间发生了一定的相互作用,土壤中有机质及其它组分会与生物炭吸附位点相互堵塞或相互竞争.添加400~700℃制备的核桃壳生物炭有利于稳定土壤中的CTZ,但溶液中CTZ浓度相对较低、添加生物炭的量相对较高时,忽略土壤与生物炭组分之间的相互作用,会高估混合体系对CTZ的吸附能力.     

生物质炭及老化过程对土壤吸附吡虫啉的影响

通过批处理恒温振荡法,系统考察了土壤类型(熟化红壤、新垦红壤)、生物质炭种类(竹炭、稻草炭)、生物质炭用量(0、0.1%和0.5%,质量分数)及老化过程(恒湿30 d)对土壤吸附吡虫啉的影响.Freundlich曲线描述的研究结果表明,有机质含量高的熟化红壤对吡虫啉的吸附能力强于有机质含量低的新垦红壤.生物质炭的添加能增强土壤对吡虫啉的吸附能力,且吸附能力随生物质炭施用量的增加而显著提高.添加等量生物质炭,新垦红壤吸附吡虫啉能力的增强效果强于熟化红壤;在同种土壤中添加不同种类的等量生物质炭,新垦红壤添加稻草炭后吸附能力更强,熟化红壤添加竹炭后吸附能力更强.恒湿老化后的处理对吡虫啉的吸附能力与新鲜处理相比明显降低,且添加竹炭的处理比稻草炭处理受老化过程影响更大.     

不同热解温度的生物炭在土壤中的矿化作用研究

为探究不同热解温度的生物炭不同组分(易降解和相对难降解碳)对其在土壤中矿化作用的影响及机理,将生物质甘蔗渣和在300、500、800℃下热解生成的生物炭(分别表示为BC300、BC500、BC800)通过水洗法剥离出碳骨架部分,然后加入含有定量土壤菌悬液的石英砂中,设置了50 d的控温培养实验并测定培养过程中不同处理样品的矿化速率.结果表明,随着热解温度从300℃升高至800℃,生物炭的易降解碳含量降低,平均停留时间从2 d增加到38 d,相对难降解碳平均停留时间从14年增加到700多年.环境温度为25℃时,碳骨架中由于缺少微生物可利用的溶解性有机碳,所以在土壤中稳定性强.环境温度升高至35℃时,温度升高提高了微生物活性,增加了碳骨架的微生物可利用部分.800℃热解生成的生物炭(BC800)及其碳骨架(W800)的累积矿化量比空白低,且即使温度升高,W800的相对难降解碳含量仍然保持最高,表明高温生物炭具有更好的固碳效果.     

菲在不同成熟度干酪根上的吸附与解吸行为

 采用热模拟的方法用云南先锋褐煤制得一组成熟度不同的干酪根,研究其对菲的吸附解吸行为.结果表明,菲在不同成熟度的干酪根上的吸附与解吸均呈现出明显的非线性和解吸滞后,并且非线性和解吸滞后程度随着干酪根成熟度的增加而增加,这与其内部结构和性质间存在一定的内在关系.     

林丹的吸附解吸行为对其沉积物基准的影响

研究了林丹在3种沉积物上的吸附/解吸行为.结果表明,在3种沉积物上的吸附等温线都符合Freundlich模型,其吸附性能受有机碳含量和颗粒分布的影响.而解吸等温线明显地偏离吸附等温线,存在显著的解吸滞后现象,解吸用二元平衡解吸(DED)模型进行拟合,效果良好.解吸不可逆程度随着沉积物中林丹初始浓度增大而增大.由DED模型推算的沉积物基准值比用线性模型推算的基准值高46倍以上.     

农药涕灭威在土壤中的不可逆吸附行为

应用多循环吸附／脱附实验法，分４个浓度范围对０～１８００ｍｇ／Ｌ深度范围内的基甲酸酯农药涕灭威在土壤中的吸附／脱附行为进行了研究，发现涕灭威在土壤中会发生不可逆吸附现象，其在土壤中的总吸队坦可由两部分组成，可逆吸附量（ｑ＾ｒｅｖ）和不可及附量（ｑ＾ｌｒｒ），其在土壤中的最大可逆吸附量（ｑｍａｘ＾ｉｒｒ）为１５２．３５ｍｇ／ｋｇ在较低浓度下，每次吸附榴有超过７０％的农药进入不可逆吸附室，但在较大浓度     

生物炭填埋场土壤覆盖层的甲烷减排性能和生物特征

覆盖土的组分与甲烷生物氧化潜力效率密切相关.将水稻秸秆生物炭与填埋场覆盖层土壤以一定的比例混合后填充入覆盖层模拟柱,形成生物炭土壤覆盖层模拟柱(RB),同时设置土壤覆盖层模拟柱(RS)为对照组,考察生物炭的添加对覆盖层的甲烷减排性能和生物特征的影响.结果表明:RB的甲烷减排性能提升较快,第81d时进气中99％的甲烷已被...     

Contribution of black carbon to nonlinearity of sorption and desorption of acetochlor on sediment

In order to investigate the contribution of various black carbon (BC) contents to nonlinearity of sorption and desorption isotherms for acetochlor on sediment, equilibrium sorption and desorption isotherms were determined to measure sorption and desorption of acetochlor in sediment amended with various amounts of BC. In this paper, two types of BC referred to as BC400 and BC500 were prepared at 400°C and 500°C, respectively. Higher preparation temperature facilitated the formation of micropores on BC to enhance its sorption capacity. Increase of the BC content obviously increased the sorption amount and reduced the desorption amount for acetochlor. When the BC500 contents in total organic carbon (TOC) increased from 0 to 60%, Freundlich sorption coefficient (K _f) increased from 4.07 to 35.74, and desorption hysteresis became gradually obvious.When the content of BC in TOC was lower than 23%, the sorption isotherm had a significant linear correlation (p = 50.05). In case of desorption, a significant nonlinear change could be observed when the content of BC was up to 13%. Increase of BC content in the sediment would result in shifting the sorption-desorption isotherms from linearity to nonlinearity, which indicated that contribution of BC to nonlinear adsorption fraction became gradually remarkable.     

Effect of dissolved organic matter on sorption and desorption of phenanthrene onto black carbon

Sorption and desorption of phenanthrene （PHE） onto black carbon （BC） extracted from sediments were studied in the presence of three types of dissolved organic matter （DOM）, including L-phenylalanine （L-PH）, peptone and citric acid. The nonlinearity of the sorption isotherms increased in the presence of DOM. The presence of L-PH reduced the sorption capacity and desorption hysteresis because of the solubilization of PHE in L-PH solution. Peptone at 50-500 mg/L also led to a decrease in sorption attributed to solubilization, although the sorbed peptone on the BC surface could slightly increase PHE sorption. Unlike L-PH and peptone, citric acid enhanced the sorption capacity and irreversibility of PHE on BC mainly due to the strong sorption of citric acid on the BC surface. Our results may help to understand the different impacts of DOM on the distribution and transport of PAH in the environment.     

Effects of temperature and surfactants on naphthalene and phenanthrene sorption by soil

Adsorption experiments were carried out to investigate the sorption behaviors of naphthalene and phenanthrene in six different soils and to determine the effects of temperature, linear alkylbenzene sulfonate (LAS) and cetylrimethyl ammonium bromide (CTAB) on sorption. The results show that for a given sorbent phenanthrene exhibited greater nonlinear and stronger sorption than naphthalene. There was a strong negative correlation for the Koc values with organic carbon content (foc). The increase of temperature was not favorable to sorption. Sorption decreased along with the increasing aqueous LAS concentration from 0 to 1000 mg/L. At low CTAB concentration (＜ 100 mg/L), the adsorption increased as CTAB hemimicelles formed on the soil surface. At high concentration, CTAB decreased the adsorption by occupying active hydrophobic adsorption sites and solubilization of naphthalene and phenanthrene.