放射性核素在海洋环境吸附体系中的固体浓度效应

通过Ag-110m在海洋沉积物中的静态吸附-解吸实验,系统地研究了放射性核素在海洋环境吸附体系中的固体浓度效应。实验结果表明:Ag-110m在海洋沉积物中的吸附-解吸等温线趋近于线性,且随着固体浓度的升高,等温线呈下降趋势,存在固体浓度效应。解吸等温线比吸附等温线滞后,固体浓度0.1~1.0g·L~(-1)范围内,吸附滞后角(θ)随着固体浓度的增加逐渐增大,不可逆性明显增强,固体浓度改变了吸附体系的不可逆性,符合"亚稳平衡吸附理论"对固体浓度效应产生机制的预测,而固体浓度达到3.0g·L~(-1)后,吸附-解吸等温线几乎重合,体系接近可逆反应。因此对于放射性核素,存在一个区间范围使得吸附体系的不可逆程度随固体浓度的增加而增大,但是超过区间的上、下限值后,体系趋近于可逆反应。应用Freundlich-SCA表面组分活度模型,用活度代替浓度,校正实际与理想吸附体系间的偏离,将不同固体浓度下的吸附-解吸实验数据分别归入同一条吸附等温线和解吸等温线,可以用来预测其他固体浓度下的吸附-解吸平衡状态。     

甲烷在特制活性炭上吸附性能

用不同的原料制得了多种高比表面的活性炭吸附剂．用标准容积法测得高压下（０～５０ＭＰａ）不同活性炭对甲烷的吸脱附等温线,得到了吸附容量和有效吸附容量．研究了温度对吸附等温线的影响．利用ＣｌａｕｓｉｕｓＣｌａｐｅｙｒｏｎ方程解析了甲烷在活性炭上的等量吸附热．结果表明,活性炭对甲烷的吸脱附存在着滞后现象,活性炭的比表面和堆密度是活性炭吸附性能的主要指标,找到了最佳甲烷吸附剂．     

大孔吸附树脂对大豆皂苷的吸附研究

比较了5种大孔吸附树脂对大豆皂苷的吸附等温线、吸附容量、解吸率和吸附动力学。发现ZTC-1树脂对大豆皂苷吸附量大、解吸容易、吸附速度快，是一种良好的大豆皂苷吸附荆，AB-8树脂次之．选择ZTC-l树脂纯化大豆皂苷粗提液，得到大豆皂苷产品纯度为78．2％(干物质)，回收率为93．1％．     

牛磺酸在大孔吸附树脂上的吸附-解吸行为研究

本文研究了S－8、D4020、NKA2、AB-8、D4006、NKA9、D3520、X－5等国产树脂对牛磺酸的吸附行为．S－8和D4020对牛磺酸的吸附能力较强,静态吸附容量在12mg／g以上．实验测定了28℃时牛磺酸在S－8和D4020上的吸附等温线,并研究了pH、盐析效应和温度对牛磺酸在S－8和D4020上吸附的影响,结果表明,温度对吸附影响很大．用80℃去离子水对吸附在树脂上的牛磺酸进行解吸,解吸率可达90％以上．     

同位素示踪法测定稀土在土壤中的吸附,解吸和扩散

对９种不同性质土壤测定结果表明，ＲＥ的吸附或解吸均与Ｌａｎｇｍｕｉｒ方程有极好的拟合性。土壤ＲＥ吸附容量在１．５－１５ｍｇ／ｇ之间，它与土壤中伊利石的相对含量呈明显正相关土壤ＲＥ解吸量与吸附量之间呈显著指数曲线关系，曲线转折点的ＲＥ吸附量称为土壤特征吸附量，以它表征ＲＥ在土壤中运移难易，比土壤吸附容量表征更有意义。     

化香树果序多酚在大孔吸附树脂上吸附特性及热力学研究

考察了7种大孔吸附树脂对化香树果序多酚的吸附容量、解吸率、吸附等温线和吸附动力学、热力学,发现L-327F树脂对化香树果序多酚吸附量大、解吸容易、吸附速度快,是一种良好的吸附剂。因此,选择L-327F树脂纯化化香树果序多酚粗提液,并经3次平行实验得到产品纯度为56.58%,回收率为49.84%。     

树脂吸附法纯化赤霉素

对比了几种大孔吸附树脂对赤霉素发酵液的吸附、解吸性能,实验发现,自制R4树脂的动态饱和吸附容量高达58.38mg/g干树脂,自制R5树脂的动态饱和吸附容量高达96.46mg/g干树脂,R5树脂的吸附容量明显高于R4,这与树脂的比表面积一致.50%(VIV)甲醇水溶液具有较好的解吸性能,收率高达95%以上,经过树脂一步吸附-解吸,赤霉素的浓度可平均提高5倍以上,集中收集最高可提高15倍以上,这对于工业化生产中,赤霉素的进一步结晶析出具有重要意义.     

活性炭纤维的微孔结构水吸附

测定了两种活性炭纤维（ACF）的氮气、水吸附等温线和XPS,研究了ACF的微孔结构和表面性质,用αs图分析氮吸附等温线获得了ACF的比表面积、微孔容量和微孔径。XPS表明在ACF表面存在多种不同结合状态的氧。水在ACF上的吸附等温线呈V型,具有很大的脱附滞后环。水通过与ACF表面的氧形成氢键发生吸附。ACF表面的初始吸附点多,则在低、中压时的水吸附量就大。     

大孔吸附树脂分离提取多杀菌素

采用大孔吸附树脂法分离提取多杀菌素.从11种大孔吸附树脂中筛选出DM11进行了静态、动态吸附性能实验,并考察了不同吸附、解吸条件的影响.结果表明,DM11的静态吸附容量为25.63mg/g(wet resin),其吸附等温线符合Langmuir吸附等温式.采用丙酮做洗脱剂,洗脱率为97.5%,动态吸附最佳吸附pH为9.5,吸附流速为6BV/h,穿透吸附容量为21.2mg/ml(wet resin),洗脱流速1.5BV/h.     

Zn(II)/α-FeOOH 吸附体系的固体浓度效应

采用宏观吸附-解吸实验系统地研究了Zn(II)在针铁矿(α-FeOOH)表面吸附的固体浓度(Cp)效应, 并考察了温度对固体浓度效应的影响, 揭示了固体浓度效应产生的机理. 实验结果表明: Zn(II)/α-FeOOH的吸附等温线随固体浓度的增加明显下移, 表现出显著的固体浓度效应; 随着固体浓度的升高, 平衡浓度相近的实验点的解吸滞后角(θ)和热力学不可逆系数(TII)均明显升高, 说明体系的可逆性随固体浓度的增大而显著降低, 这一结果符合亚稳平衡吸附(MEA)理论对固体浓度效应产生机制的预测. 本研究还发现Zn(II)/α-FeOOH体系在低温下的固体浓度效应比在高温下更为显著. 不同温度下的吸附-解吸实验表明,该体系的吸附可逆性随温度的升高而明显增强(θ和TII明显降低), 这再次证明了吸附可逆性对Cp效应的控制作用, 并从另一角度证实了MEA理论对固体浓度效应机制的解释. 实验测得Zn(II)/α-FeOOH体系的吸附热力学参数△H、△S分别为34.07 kJ·mol-1和195.71 J·mol-1·K-1, 表明Zn(II)可在针铁矿表面发生吸热的化学吸附反应.     

胡敏酸的结构特征及其吸附行为

使用0.5mol/L NaOH和0.1mol/L Na_4P_2O_7溶液分别从土壤中提取胡敏酸,并且对其进行了元素分析、红外光谱、固态13C核磁共振的定性、定量研究。结果表明,两种胡敏酸的性质很相似,但也存在一些微小差异,Na_4P_2O_7提取的胡敏酸比NaOH提取的具有芳香度较大、聚合度较高、极性官能团含量较多的特点。测定了菲在6个胡敏酸上的吸附等温线,Freundlich模型很好的拟合了所有吸附等温线,相关系数r均在0.992以上。有机碳分配系数K_(oc)与胡敏酸中极性碳(POC)之间存在明显的线性相关关系,并受到提取剂类型的影响。     

Sorption and desorption of radiocesium on calcareous soil: Results from batch and column investigations

The sorption and desorption of radiocesium on a calcareous soil from Jiuqian County of Gansu Province (China) were studied by using batch and column experiments. The sorption-desorption isotherms and the breakthrough curves, displacement curves on the whole soil and two treated soils were determined. Based on these results, it was found that the sorption and retention of cesium are mainly determined by the clay minerals, that the sorption-desorption hysteresis of cesium on the calcareous soil is obvious and that the organic matter has a little positive contribution and the calcium carbonate has a little negative contribution to the sorption of cesium on the whole soil. The results from batch experiments were consistent with the results from column experiments.     

Use of 13C to monitor soil organic matter transformations caused by a simulated forest fire

Soil organic matter (SOM) transformations caused by heating were analyzed using the stable carbon isotope (13)C as a tracer to follow C mineralization dynamics and C transfers between different organic compartments. A (13)C-labelled soil, obtained by incorporation of (13)C-enriched Lolium perenne phytomass into a pine forest soil, was heated for 10 min at 385 degrees C to reproduce conditions typical of a forest fire and changes in total C content, potential C mineralization activity and C distribution between the different soil organic fractions were determined. Changes caused by heating on the potential soil C mineralization, determined by laboratory aerobic incubation, reveal alterations to the SOM biodegradability; some stabilized SOM showed an increase in biodegradability, whereas less stabilized SOM became more resistant to microorganisms. Chemical fractionations of SOM allowed us to monitor changes in its composition. As a consequence of heating, the less polymerized humic fractions were the most strongly affected, with the total disappearance of fulvic acids. A significant increase in the quantity and degree of polymerization of the humic acids at the expense of other more (13)C-enriched substances was also found. Finally, a large decrease in humin was observed, its solubilizable part disappearing completely, probably as a consequence of the incorporation of the byproducts into the free organic matter fraction.     

Sorption and desorption of radioselenium on red earth and its solid components

The effect of organic matter and iron oxides as solid components of the red earth on the retention of SeO₃ has been investigated by a batch technique and selective extraction method. The sorption and desorption isotherms of SeO₃ on the untreated red earth and the three treated soils were determined at 20°C, pH 6.8 or 7.2 and in the presence of 0.01M CaCl₂. It was found that the sorption-desorption hysteresis for untreated an treated soils is obvious and the clays play an important role in the sorption-desorption hysteresis, and that the retention of SeO₃ on red earth is attributed to the iron oxides to a great extent.     

Sorption and desorption of radioiodine on calcareous soil and its solid components

The effect of different solid components of calcareous soil on the retention of I was investigated by a batch technique and selective extraction method, and the effect of -irradiation was also investigated. The sorption and desorption isotherms of I on the one untreated, three treated soils and the calcareous soil irradiated with -rays were determined at 30 °C, pH 8.1±0.2 and in the presence of 1.0×10^–4M or 0.67×10^–5M CaCl₂. It was found that the sorption-desorption hysteresis on the calcareous soil actually occurs on the same time scale, that iodine can be easily transported in the calcareous soil and that the exceptionally high contribution of organic matter to the iodine sorption is demonstrated.     

Characterization of soil organic matter fractions from grassland and cultivated soils via C content and delta13C signature

Variations in (13)C natural abundance and distribution of total C among five size and density fractions of soil organic matter, water soluble organic C (WSOC) and microbial biomass C (MBC) were investigated in the upper layer (0-20 cm) of a continuous grassland soil (CG, C(3) vegetation), a C(3)-humus soil converted to continuous maize cultivation (CM, C(4) vegetation) and a C(3)-humus soil converted to a rotation of maize cultivation and grassland (R). The amounts of WSOC and MBC were both significantly larger in the CG than in the CM and the R. In the three soils, WSOC was depleted while MBC was enriched in (13)C as compared with whole soil C. The relative contributions to the total C content of C stored in the macro-organic matter and in the size fraction 50-150 microm decreased with decreasing total C contents in the order CG > R > CM, while the relative contribution of C associated with the clay- and silt-sized fraction <50 microm increased. This reflects a greater stability and physical protection against microbial degradation associated with soil disruption (tillage) of the clay- and silt-associated organic C, in relation to the organic C in larger size fractions. The size and density fractions from the CG soil showed significant differences in (13)C enrichment, indicating different degrees of microbial degradation and stability of soil organic C associated with physically different soil organic matter (SOM) fractions. Delta(13)C analysis of the size and density fractions from CM and R soils reflected a decreasing turnover rate of soil organic C with increasing density among the macro-organic matter fractions and with decreasing particle size.     

Effect of phosphate on phenanthrene sorption in soils

Phosphate is ubiquitous in the environment. However, its impact on sorption of hydrophobic organic compounds in soils has received little attention. Some effects of phosphate on phenanthrene sorption were investigated in this study using two Chinese soils with contrasting properties. The presence of phosphate significantly decreased the capacity and increased the nonlinearity of phenanthrene sorption in the soils, and this sorption-inhibiting effect was more significant at high phosphate concentration. The influence of phosphate on phenanthrene sorption in the soils was governed by the release of dissolved organic carbon (DOC), particularly higher-molecular-weight and highly aromatic DOC, which tended to be enhanced in the presence of phosphate (p<0.01) as evidenced by size exclusion chromatography and specific UV absorbance analysis. Atomic force microscopy and ζ potential analysis reveal that the ringed microaggregates of DOC were disrupted into larger condensed microaggregates and the solid interfaces tended to be more hydrophilic in the presence of phosphate which also inhibited the accumulation of phenanthrene in the soils. This study for the first time points to an important role of phosphate in the sorption of phenanthrene in soils and provides substantial evidence for the mechanisms involved using a combination of microscopic and chromatographic techniques.     

Application of pyrolysis-gas chromatography/mass spectrometry to study changes in the organic matter of macro- and microaggregates of a Mediterranean soil upon heating

The heating effect on the soil organic matter (SOM) of a Mediterranean soil was studied in two fractions (macro- and microaggregates) and in two environments (soil under canopy of Quercus coccifera and bare soil between plants). Samples were heated under laboratory conditions at different temperatures (220, 380 and 500°C) to establish their effects on the SOM quality and quantity by comparison with unheated control samples (25°C). The SOM content in the soil under canopy was higher than in the bare one and in the microaggregate fractions than in the macroaggregate ones. Increasing temperatures caused, in general, the decrease of SOM content in both soils as well as in both aggregate classes. The quality of SOM was determined after extraction with 0.1 M NaOH and analysed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Obtained pyrolysates were characterized by the presence of polyphenols and other aromatic pyrolysis products (lipids, polysaccharides, proteins and lignin derivatives). Some of the products in these control samples, and furthermore the presence of black carbon (BC) markers (e.g. benzene, pyridine and toluene), confirmed the occurrence of past wildfires in the study zone. The composition of the SOM extracted from the soils heated at 220°C, was quite similar to that obtained from unheated soils. The products derived from polysaccharides and lignin, and some coming from polyphenols, were not detected in the pyrolysates of the soil heated at 380 and 500°C.     

Application of scanning calorimetry to estimate soil organic matter loss after fires

The severe heating of soil during wildfires and prescribed burns may result in adverse effects on soil fertility due to organic matter loss. No rapid and reliable procedure exists to evaluate soil organic matter (SOM) losses due to heating. Enthalpy of SOM combustion correlates with organic matter content. Quartz is a ubiquitous mineral in soils and has a remarkably constant composition and reversible α–β phase transition at 575 °C. We suggest that SOM content in heated and unheated soils can be compared using the ratio of SOM combustion enthalpy on heating to the β–α quartz transition enthalpy measured on cooling of the same sample. This eliminates the need to dry and weigh the samples, making possible field applications of the proposed method. The feasibility of using the (ΔH _{comb SOM})/(ΔH _β–α Qz) ratio was established with experiments on soil samples heated in the laboratory and the method was then used for evaluation of SOM loss on two pile burn sites at UC Berkeley’s Blodgett Forest Research Station in Georgetown, California.     

Sorption and desorption of phenanthrene onto iron, copper, and silicon dioxide nanoparticles

The sorption and desorption of phenanthrene by three engineered nanoparticles including nanosize zerovalent iron (NZVI), copper (NZVC), and silicon dioxide (NSiO2) were investigated. The sorption of phenanthrene onto NSiO2 was linear and reversible due to the hydrophilic properties of NSiO2. In comparison, sorption of phenanthrene onto NZVI and NZVC was nonlinear and irreversible, which was potentially due to the existence of significantly heterogeneous surface energy distribution patterns detected by a standard molecular probe technique. Naphthalene exerted significant competitive sorption with phenanthrene for NZVI and NZVC, and the isotherm of phenanthrene changed from being significantly nonlinear to nearly linear when naphthalene was simultaneously absorbed. A surface adsorption mechanism was proposed to explain the observed sorption and competition of phenanthrene on both NZVI and NZVC. In contrast, no competition was observed for sorption onto NSiO2. The sorption of phenanthrene on all three nanoparticles significantly decreased with increasing pH. The sorption irreversibility of phenanthrene on NZVI and NZVC were significantly enhanced with decreasing pH. A pH-dependent hydrophobic effect and dipole interactions between the charged surface (electron acceptors) and phenanthrene with electron-rich pi systems (electron donors) were proposed to explain the observed pH-dependent sorption.