热解温度对花生壳生物质炭吸附去除水中4-硝基酚的影响

为提升农业废弃物的资源化再利用价值,以花生壳为原料,在不同热解温度(400、500、600℃)下限氧制备花生壳生物质炭(BC400、BC500、BC600),考察其对水中4-硝基酚的吸附效果。生物质炭表面灰分通过酸洗法去除,采用批量吸附试验的方法分析生物质炭对PNP吸附特性的影响,并结合元素分析、扫描电镜及红外光谱图方法,探讨热解温度对生物质炭吸附水中PNP特性的影响。结果表明,生物质炭总产量随温度升高而降低,其含碳量随温度升高逐渐增加;生物质炭中含氧官能团随温度的升高而减少,芳香性增强,有利于对有机物的吸附。吸附等温线符合Freundlich模型,线性拟合很好,R2在0.954～0.991之间;对比伪二级动力学模型、Elovich模型、颗粒内扩散模型可知,吸附过程与伪二级吸附动力学模型拟合效果最佳, R2在0.981～0.999之间,平衡吸附量随热解温度升高而增大,BC600BC500BC400,BC600的吸附容量为34.48 mg/g,是BC400的2.25倍。以NaOH为解吸剂,当NaOH质量浓度为1.0 mg/L时对4-硝基酚的解吸效率最高,为68.21%,可见生物质炭的再生利用具有一定的可行性。因此,高温制备的花生壳生物质炭可作为去除4-硝基酚的良好功能材料。     

不同热解温度制备的水稻秸秆生物炭理化特性分析

以不同热解温度(100～800℃)制备的水稻秸秆生物炭为研究对象,研究在不同热解温度下制成的生物炭的理化特性。结果表明,热解温度为100～300℃制成的水稻秸秆生物炭呈弱酸性,400℃以上时呈碱性;水稻秸秆生物炭表面碱性含氧官能团数量随着热解温度的升高而增加、酸性含氧官能团则减少;水稻秸秆生物炭中的官能团C=C、C-O-C、-OH和-C=O在较高的热解温度下发生缔合或消除,促进了芳香基团的形成;随着热解温度的升高,水稻秸秆生物炭的阳离子交换量(CEC)、比表面积、孔径、比孔容、氮气吸附量和颗粒表面的分型维数(D1)均先增加后降低,阳离子交换量(CEC)在300～500℃时、其它性状在400～600℃之间达到最大值;以不同热解温度制成的水稻秸秆生物炭颗粒的孔隙结构均以孔隙宽度2～50 nm的中孔为主。随热解温度的升高,水稻秸秆生物炭的产率逐渐降低;400～500℃炭化2 h,生物炭产率最高,其孔隙结构最为复杂,所以可以认为400～500℃是水稻秸秆炭化的最佳温度。     

小麦秸秆生物炭对高氯代苯的吸附过程与机制研究

以小麦秸秆为原料,分别在三种温度(400℃、500℃、600℃)下制备小麦秸秆生物炭,并标记为WSB400、WSB500、WSB600。分析了秸秆炭的元素组成,表征了其结构和表面特征,研究了秸秆炭对五氯苯和六氯苯的吸附动力学和吸附等温线。结果表明,升温热解使得小麦秸秆有机组分炭化、极性官能团消除,炭化程度增强;三种秸秆炭均可快速高效地吸附高氯代苯,且对六氯苯的吸附要快于五氯苯,假二级动力学方程能更好地拟合秸秆炭对氯苯的吸附动力学过程;不同秸秆炭对氯苯的饱和吸附量大小顺序为WSB400WSB500WSB600;对吸附等温线进行分析可得,随着秸秆炭制备温度的升高,其对氯苯的吸附等温曲线由线性变为非线性,吸附机理则由以分配作用为主过渡到分配作用与表面吸附共同作用。     

皇竹草生物炭的结构特征及其对（）的吸附性能

以皇竹草茎秆为原料,在限氧控温（300、500、700℃）条件下制备生物炭,研究该生物炭的结构特征及其对Cr（Ⅵ）的吸附行为。结果发现,随着热解温度的升高,皇竹草生物炭的产率下降,而灰分、pH呈上升趋势;电镜扫描（SEM）观察可见不同热解温度下所制备的生物炭结构相似,均具多孔和管状结构,但在700℃条件下所制备的生物炭相对300℃下制备的生物炭孔壁变薄,且孔壁有附着物,切面有突起结构。三种温度下制备的皇竹草生物炭对溶液中的Cr（Ⅵ）都具有较好的吸附作用,且500、700℃下制备的生物炭比300℃下制备的生物炭具有更好的吸附效果。在0~1 h之间,三种热解温度下制备的生物炭对铬的吸附量均随着时间的延长而快速增加,当吸附至1h时,基本达到饱和状态,随后吸附量无明显变化。     

溶液初始pH值及裂解温度对玉米秸秆基生物炭吸附Cr（遇）的影响

以玉米秸秆为原料,在300、450益和600益下裂解得到3种生物炭,通过批处理实验讨论了溶液初始pH值和裂解温度对玉米秸秆及其生物炭吸附Cr（遇）的影响,并用吸附动力学模型和等温吸附模型对实验结果进行拟合。结果表明：对于同种吸附材料而言,溶液初始pH值越低,玉米秸秆及其生物炭对Cr（遇）的吸附量越大;当溶液初始pH值为3或5时,对Cr（遇）的吸附性能大小顺序为：玉米秸秆>生物炭300益>生物炭450益>生物炭600益;当溶液初始pH=1时,对Cr（遇）的吸附性能大小顺序为：生物炭300益>玉米秸秆>生物炭450益>生物炭600益,且生物炭300益对Cr（遇）的最大吸附量约为141.24 mg·g-1。可见,溶液初始pH值越低,生物炭的裂解温度越低,越有利于生物炭对Cr（遇）的吸附。     

水稻秸秆生物质炭对土壤磷吸附影响的研究

本文以水稻秸秆为原料,分析了不同热解温度下生物炭的性质,并利用批处理实验,分析了生物炭添加量和热解温度对土壤磷吸附特性的影响。结果表明：随着热解温度的升高,生物炭的碳化程度、比表面积和磷含量增加。生物炭添加显著减少了土壤对磷的吸附量,而且随着生物炭热解温度的增加,土壤对磷的吸附量显著增加。Langmuir方程和Freundlich方程都能够较好地拟合生物炭对土壤磷的等温吸附。准一级动力学方程和准二级动力学方程可较好地描述生物炭对土壤磷吸附动力学的行为。通过以上研究结果可知,水稻秸秆生物炭可以减少土壤对磷的吸附并增加土壤有效磷的含量,因此在土壤改良方面具有一定的应用潜力。     

碳酸钾添加比例对玉米秸秆生物炭表面特性的影响

在600℃的热解温度下通过添加不同比例的碳酸钾制备活性生物炭。对比分析了碳酸钾活化生物炭(KBC)和普通生物炭(BC)的特性,包括生物炭红外光谱特征、表面官能团、比表面积和孔径分布及吸附动力学过程等。结果表明,经碳酸钾活化的生物炭比表面积大为提高,最高达到566 m2 g-1(KBC-2-600),而普通生物炭(BC600)的比表面积仅为86.8 m2 g-1,KBC600系列的介孔容积和微孔容积均显著高于BC600,介孔容积平均扩大了16倍,微孔容积平均扩大了4倍,同时提高了微孔率。经碳酸钾活化的生物炭表面官能团的数量和饱和度发生改变,在1 256 cm-1~3 414 cm-1处,官能团的总体含量均低于普通生物炭,酯类羰基消失,形成氢键的能力减弱,非饱和醚类增加,芳香性和非极性提高,此表面特征更有利于吸附非极性芳香类污染物。对萘吸附的动力学实验表明,BC600和KBC-4-600均适合以二级动力学模型拟合,经碳酸钾活化后,生物炭的吸附性能提高,颗粒内扩散模型拟合结果表明,经碳酸钾活化后,生物炭内部孔隙复杂程度和数量均得到提高。碳酸钾活化的生物炭表面性质优良,作为高效吸附剂用于修复非极性芳香类污染有很大潜力。     

碳酸钾添加比例对玉米秸秆生物炭表面特性的影响

在600 oC的热解温度下通过添加不同比例的碳酸钾制备活性生物炭。对比分析了碳酸钾活化生物炭（KBC）和普通生物炭（BC）的特性,包括生物炭红外光谱特征、表面官能团、比表面积和孔径分布及吸附动力学过程等。结果表明,经碳酸钾活化的生物炭比表面积大为提高,最高达到566 m2?g-1（KBC-2-600）,而普通生物炭（BC600）的比表面积仅为86.8 m2?g-1,KBC600系列的介孔孔容和微孔孔容均显著的高于BC600,介孔孔容平均扩大了16倍,微孔孔容平均扩大了4倍,同时提高了微孔率。经碳酸钾活化的生物炭表面官能团的数量和饱和度发生改变,在1 256 cm-1～3 414 cm-1处,官能团的总体含量均低于普通生物炭,酯类羰基消失,形成氢键的能力减弱,非饱和醚类增加,芳香性和非极性提高,此表面特征更有利于吸附非极性芳香类污染物。对萘吸附的动力学实验表明,BC600和KBC-4-600均适合拟二级动力学模型拟合,经碳酸钾活化后,生物炭的吸附性能提高,颗粒内扩散模型拟合结果表明,经碳酸钾活化后,生物炭内部孔隙复杂程度和数量均得到提高。碳酸钾活化的生物炭表面性质优良,作为高效吸附剂用于修复非极性芳香类污染有很大潜力。     

木屑生物质炭对水中阿特拉津、多菌灵和啶虫脒复合农药的吸附性能研究

选取木屑为原材料,在500、700℃下制备生物质炭(标记为MX500和MX700),试验考察了溶液初始pH和生物质炭投加量对其吸附性能的影响,并利用吸附动力学、吸附等温线以及傅里叶变换红外光谱(FTIR)等手段,研究了木屑生物质炭对水溶液中3种不同类型的典型常用农药阿特拉津(ATR)、多菌灵(CAR)和啶虫脒(ACE)的吸附特性及吸附机理。结果表明：热解温度700℃,pH 3.0,生物质炭投加量为2.0 g/L时,木屑生物质炭对3种农药的联合吸附效果最好。MX700对ATR、CAR和ACE的最大吸附量分别为40.2、50.4和44.9μg/g,约为MX500的1.4倍～2.2倍。吸附动力学和吸附等温线结果显示,准二级动力学方程、颗粒内扩散方程和Langmuir方程能较好地拟合吸附过程。FTIR结果显示,木屑生物质炭主要通过酚羟基和羧基等含氧官能团以及芳香环结构去除水中ATR、CAR和ACE。木屑生物质炭对农药的吸附机理包括静电作用力、氢键作用力及π–π键相互作用力。在100μg/L浓度下,木屑生物质炭对ATR、CAR和ACE复合农药的吸附效果和机理与农药单体类似。综上,木屑生物质炭作为...     

刺桐生物炭对水中氨氮和磷的吸附

本研究以园林绿化废弃物刺桐为原料,在不同的热解温度下(300、500、700℃)制备生物炭,用动力学方程和等温吸附方程分别拟合生物炭对氨氮和磷的吸附性能。等温吸附方程拟合结果表明:生物炭对水中氨氮和磷的吸附量均随着氨氮和磷的初始浓度的增加而增大,且均能较好地拟合Langmuir吸附方程,且BC500吸附效果最好;动力学方程拟合结果表明:不同热解温度下得到的生物炭对氨氮和磷的吸附速率较快的过程分别发生在最初的300 min和60 min内,且均能较好地拟合准二级动力学方程;此外,生物炭对不同初始p H下对氨氮和磷溶液的吸附效果分别为p H7p H11p H3和p H11p H7p H3。     

Predicting mobility of alkylimidazolium ionic liquids in soils

Background, aim, and scope  Ionic liquids (ILs) are a new class of alternative solvents that make ideal non-volatile media for a variety of industrial processes such as organic synthesis and biocatalysis, as alternative electrolytes, as phases and phase modifications in separation techniques, and as alternative lubricants. Once the large-scale implementation of ILs begins, the industrial application will follow. In view of their great stability, they could slip through classical treatment systems to become persistent components of the environment, where the long-term consequences of their presence are still unknown. Sorption on soils has a critical effect on the transport, reactivity, and bioavailability of organic compounds in the environment. So far, the IL sorption mechanism was investigated solely on the basis of batch experiments, which precluded any assessment of the dynamics of the process. An understanding of the mobility of ILs in soil columns is crucial for an accurate prediction of their fate in the soil. The aim of this study therefore was to investigate in detail the mobility of selected imidazolium ILs on three soil types. Moreover, it was decided to study these processes in soils from the coastal region (Gdańsk, Poland), which usually constitute a very important geochemical compartment, participating in the transport of contaminants on their way to the sea. Materials and methods  The mobility of alkylimidazolium ILs was investigated in columns containing soils from the coastal area. In addition, the sorption processes in all the soil systems studied were described isothermally and the equilibrium sorption coefficient was evaluated. The sorption capacities were determined according to OECD guidelines. Sorption dynamics was studied with use of polypropylene columns (diameter—10 mm, height—100 mm) packed with 10 g of soil. The ionic liquid solution was then injected into the soil column and left for 24 h to equilibrate. After this, a solution of 0.01 mM CaCl₂ was pumped through the column at a rate of 0.3 ml min^–1. Effluents were collected from the bottom of the column and analyzed by HPLC. Results  Sorption was strongest on the Miocene silt and the alluvial agricultural soil and weakest on the podsolic soil and Warthanian glacial till. The K _d value of long-chain ILs was far higher than that of the short-chain ones. Among the substances tested, hydroxylated ILs were usually more weakly sorbed. Desorption of ILs is inversely correlated with sorption intensity. The experimental results of the column tests correlate well with those from batch experiments. In the cases of weakly binding soils, ILs were detected almost immediately in the eluent. The elution profiles of long-chain ILs indicate that these compounds are very strongly sorbed onto most soils, although certain amounts were transported through the soil. ILs exhibit a certain mobility in soils: in particular, salts with short and/or hydroxylated side chains are extremely mobile. Discussion  The results indicate a stronger binding of ILs in the first sorption layer; once the first layer is saturated, there are no more active sites on the soil surface (no free charged groups); hence, there are no more strong electrostatic binding sites, and dispersive interaction becomes the dominant interaction potential. The influence of the structure of the ILs, especially the side-chain length was also confirmed: The K _d value of long-chain ILs was far higher than that of the short-chain ones. The long alkyl side chain facilitates dispersive interactions with soil organic matter and intermolecular binding, and the build-up of a second layer becomes possible. Among the substances tested, hydroxylated ILs were usually more weakly sorbed. The hydroxyl group in the side chain can alter the polarity of the compound so strongly that interaction with organic matter hardly occurs; these salts then remain in the aqueous phase. The experimental results from the column tests correlate well with those from batch tests. In the weakly binding soils (with low organic matter), the only binding to the soil surface must be via electrostatic interactions, although intermolecular van der Waals (ionic liquid–ionic liquid) interactions could also be taking place. The elution profile maxima for organic rich soils are far smaller than for the other soils. In the former, hydrogen bonding, dispersive and π…π interactions play a more important part than electrostatic interactions. The rapidly “disappearing” maxima of the elution peaks may indicate that, after elution of ILs from the second layer, it is difficult to extract further sorbed ILs. In the first layer, the ILs are bound by much stronger electrostatic interactions. To break these bonds, a greater energy is required than that sufficient to extract ILs from double sorption layers. Results indicate, moreover, that hydrophobic ILs will be sorbed in the first few centimeters of the soil; migration into the soil will therefore be almost negligible. Conclusions  Sorption of ILs was the strongest in soils with the highest cation exchange capacities and a high organic content. ILs were also more strongly bound to the first sorption layer. The sorption coefficients of long-chain ILs were far higher than those of short-chain ones; usually, hydroxylated derivatives were the least strongly sorbed. Results of soil column experiments to investigate the mobility of ILs in soils correlated well with those from batch tests, and the elution profiles were also well correlated with organic matter content. The observed rapidly disappearing elution peak maxima probably indicate that, after elution of the ILs from the second layer, it is difficult to extract further sorbed compounds. Recommendations and perspectives  Obtained results gave an interesting insight into mobility of ionic liquids in soil columns. However, several questions are now opened. It is therefore necessary to undertake further studies focused on total cycle of ionic liquids in the soil environment. This should include their evapotrasporation (lysimeter test), bioaccumulation by plants as well as degradation and transformation processes (chemical, biological, and physical) typically occurring in soils. Moreover, a further risk assessment of ILs is desirable since this study has indicated that these compounds, especially those with low lipophilicities, are generally mobile in the soil matrix. It is already known that short-chain ILs are characterized by low toxicities; should they enter the environment, they will probably migrate within the soil and pose a risk of contamination of surface and ground waters. This topic is relevant to the audience. Environmental threat of short-chain ionic liquids is currently unknown. From the predictive point of view, judging on known low acute toxic effects or high polarities of these compounds seems to be not enough to confirm their “environmental friendliness”. If we are to fully understand the potential environmental effects, one should also have an insight into long-term biological consequences of these ionic liquids, including chronic toxicity tests, bioaccumulation, and biotransformation rates as well as stability against natural elimination mechanisms.     

Sorption of methyl-parathion and carbaryl by an organo-bentonite

The modification of bentonite clays by cetyltrimethylammonium bromide (CTMAB) surfactant via cation-exchange produces materials (“organo-clays”) with an increased capacity for sorbing organic compounds such as pesticides. The sorption from solutions of two nonionic pesticides, methyl-parathion and carbaryl, by an organo-bentonite has been investigated. The pesticides are partitioned into the surfactant. The distribution coefficients, K _ss, show a strong dependence on surfactant loading of the bentonite. The surfactant configuration at the clay surface has a marked influence on the effective volume and density of the bound surfactant. At low surfactant loadings, the K _ss values increased, reached a maximum, and then decreased as the extent of loading increased. At low loading levels, the surfactant appears to form a monolayer (organic film) that effectively adsorbs the pesticides, resulting in very high K _ss values. At high loadings, the sorbed surfactant appears to form a bulk-like medium that behaves essentially as a distribution phase. As a result, the K _ss values decreased appreciably, and became less dependent on the CTMAB loading. Moreover, when the surfactant concentration in water was greater than the critical micelle concentration, the surfactant uptake on the clay reaches a plateau and an increasing fraction of the micelles remain in solution, together with the pesticides which bound to them. The competition for the pesticides between the aqueous micelles and the sorbed surfactant leads to a decrease in distribution coefficients.     

铬在土壤中的吸附解吸研究进展

对铬在土壤中的吸附解吸研究进行了综述,土壤中铬的吸附解吸机理包括非专性吸附(离子交换吸附)、专性吸附以及物理表面吸附,分别对pH、氧化还原电位、土壤组分(土壤矿物和有机质)、竞争离子以及离子强度等因素对铬吸附解吸的影响作了论述。文章进一步描述了土壤中铬吸附解吸的数学模型Freundlich方程、Langmuir方程、一级动力学模型、金属-腐殖酸模型(one-sitemodel)和表面络合模型-扩散层模型(DLM)等的研究情况,并对今后的研究方向进行了探讨。     

土壤吸附铜离子的研究进展

对土壤吸附Cu的研究进行了综述。主要讨论了吸附速率,吸附等温线,表面络合模式和影响吸附量的因子等方面的问题。目前对土壤吸附Cu的速率研究主要有两种方法:一是根据实验数据绘制吸附量随时间变化的曲线,根据所绘制的曲线斜率来研究吸附动力学过程;二是选择经验性的化学动力学方程对数据进行拟和,依据较高的相关系数和较低的标准误差选择最优方程,根据吸附速率系数来进行定量的研究。土壤对Cu吸附的定量描述,经验性的吸附等温式仍不失为一个十分有用的方法;考虑到土壤性质和环境因子对吸附的影响,模型中应该加入这些参数使其更能反映土壤对重金属的吸附过程,但这方面的研究相对较少。土壤表面电荷特征、低分子有机酸对土壤吸附Cu的影响和吸附过程中Cu形态的变化等方面研究也较少。     

汞在泥炭上的吸附特征研究

采用批次法研究了汞在三江平原泥炭、吉林双阳泥炭上等温吸附特征及介质pH值、背景离子浓度的影响。实验结果表明:两种泥炭吸附等温线均同时符合Langmuir和Freundlich等温吸附方程,而与Langmuir方程的拟合效果更好; 在溶液汞浓度相同时,温度升高,泥炭对汞的吸附量降低;在相同的条件下,三江平原泥炭对汞的吸附量大于吉林双阳泥炭对汞的吸附量;两种泥炭对汞的吸附量受pH值的影响明显且都在pH 6.0左右具有最大的吸附量;在酸性条件下,吸附介质的pH值升高利于泥炭对汞的吸附;介质的离子浓度升高,可以使两种泥炭对汞的吸附量迅速降低。     

Boron sorption isotherm: A method to estimate boron fertilizer requirement

Abstract

The boron sorption isotherm method of soil testing may provide an estimate of the fertilizer required to bring the soil to an optimum boron level. Data from the boron isotherm experiment suggests that at low concentrations a plot of added boron vs equilibrium solution boron will be linear. The boron concentration at which this plot becomes linear will depend on the characteristics of the soil tested. The data, from this and other studies, suggest that 0.5 ppm boron in the equilibrium solution should be the approximate upper limit of boron concentration where this relationship is linear. Since boron added is linear with respect to boron in equilibrium solution, boron fertilizer required to adjust the equilibrium solution concentration can be calculated from the least squares regression equation of these two variables. This fertilizer requirement can only be determined when the optimum level of boron in equilibrium solution is known. Thus, further study is needed to establish this optimum level for all plant species.     

氟喹诺酮类抗生素在农业紫色土中的吸附研究

抗生素被广泛作为抗菌药物和添加剂使用在畜牧业中,造成大量抗生素随着动物粪便进入到土壤环境。吸附行为是抗生素在土壤中迁移转化的重要过程,对抗生素的风险评估及污染控制具有重要的意义。本文采用吸附试验研究了两种氟喹诺酮类抗生素(诺氟沙星(NOR)和氧氟沙星(OFL))在重庆广泛分布的紫色土中的吸附特性以及影响因素。结果表明:NOR和OFL在紫色土上的吸附过程较快,5 h就能达到吸附平衡,吸附常数Kd能达到3 082 L/kg。Freundlich吸附等温模型能很好拟合紫色土对NOR和OFL的等温吸附过程。由吸附过程的吉布斯自由能ΔG和吸附能E可知,紫色土吸附NOR和OFL主要是通过物理吸附。溶液pH6会降低紫色土对NOR和OFL的吸附。当溶液离子强度从0.005 mol/L增加至0.05 mol/L时,NOR和OFL在紫色土上的吸附量分别降低了10.2%和11.7%。土壤有机质对NOR和OFL的吸附过程影响很小。     

Sorption–desorption of phenolic acids as affected by soil properties

Phenolic acids have been implicated in the process of allelopathy and are, therefore, of interest in plant management as a basis for new herbicide structures. The potential bioavailability of phenolic acids is controlled by sorption–desorption processes in soil. Sorption–desorption of p-coumaric acid (4-hydroxycinnamic acid), ferulic acid (3-methoxy-4-hydroxycinnamic acid), veratric acid (3,4-dimethoxybenzoic acid), vanillic acid (3-methoxy-4-hydroxybenzoic acid), and p-hydroxybenzoic acid (4-hydroxybenzoic acid) was characterized on soils with varying physicochemical properties. The phenolic acids sorbed quickly (<8 h) and in high proportions to the amount applied (average 84% of applied was sorbed). Sorption was irreversible with the batch desorption method used (0.01 N CaCl₂ extraction). Pretreatment of soils to remove organic matter and free metal oxides from the soils decreased sorption, particularly in soils with free oxides removed. Statistical analysis suggested that sorption of p-coumaric and ferulic acids was correlated with soil clay content and veratric acid sorption was correlated with several soil factors. In contrast, no consistent relationship between soil characteristics and vanillic and p-hydroxybenzoic acid sorption was found. Based on the results of these experiments, i.e. the high reactivity of the phenolic acids, it is unlikely that these chemicals would be transported far from their point of origin, limiting their range of influence. It appears that, for phenolic acids to have allelopathic effects on plants, they would have to persist in the soil for long periods, resulting in a buildup of the chemical to high enough levels so that sufficient chemical would be in solution to cause the allelopathic effects, even though they may be strongly sorbed at lower concentrations.     

Phosphate desorption studies on three highly weathered tropical soils

Abstract

Phosphate (P) desorption studies were carried out on two ultisols and an oxisol. The desorption patterns were observed at five levels of P concentration (5, 10, 15, 20 and 25 mg P/ml). Three desorption phases are described.