Dynamics of arsenic-containing compounds sorption on sediments

Background  River and lake sediments constitute complex and difficult analytical samples. On the other hand, sediments play a fundamental role in the distribution of toxic compounds in aquatic systems and in the evaluation of the current state and the course of changes taking place in the environment. Among elements present in the environment in trace concentrations, but having well-elaborated toxic properties, one of most dangerous is arsenic. The element occurs in the environment in several chemical forms, predominant are inorganic forms of As(V) and As(III), and methylated forms such as monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA). Objectives  Reported herein are experiments, which were undertaken with the aim of examining the dynamics of arsenic sorption in sediments and its dependence on speciation of the element and the pH in the environment. Simultaneously, influence of organic matter content and chemical composition of the sediments on As sorption, were investigated. Methods  Sediment samples (upper 10 cm layer) were collected from three sites located in the vicinity of Cracow:

黄土高原干旱半干旱区生物结皮覆盖土壤水汽吸附与凝结特征

生物结皮是一种广泛分布于干旱半干旱地区土壤表层的特殊复合体,为揭示其对土壤水汽吸附与凝结过程的影响,该研究通过室内定量水汽吸附试验和野外对水汽凝结的连续观测,对黄土高原典型生物结皮(藻结皮、藻藓混生结皮、藓结皮)与裸沙的水汽吸附和凝结特征进行对比研究。结果表明:生物结皮的覆盖显著提升了表层土壤的水汽吸附能力,其平均水汽吸附量比裸沙高66.7%。不同类型生物结皮水汽吸附能力差异显著,表现为藓结皮最高,混生结皮次之,而藻结皮最低。GAB(Guggenheim-Anderson-de Boer)吸附模型能较好的描述生物结皮土壤水汽吸附与解吸附过程,模拟结果决定系数R20.99、均方根误差RMSE0.001 2 g/g及平均相对偏差百分比E16.0%;此外,生物结皮加剧了土壤水汽吸附与解吸附曲线之间的滞后效应,其滞后指数平均是裸沙的2.0～2.9倍。水汽凝结结果显示,水汽凝结过程均受气温与相对湿度等气象因子制约,且生物结皮覆盖下表层土壤的水汽凝结和蒸发过程相较于裸沙更为迅速。同时,生物结皮的日均水汽凝结量是裸沙的1.6～1.8倍。综上,干旱和半干旱地区生物结皮覆盖显著提高了表层土壤的水汽吸附能力、并增加了水汽凝结量,对区域表层土壤的水分运动过程产生了重要影响。     

异龄林的生长动态研究

以线性为基础的矩阵模型和非线性模型,一直都被相互独立地用来模拟林分的生长动态。本文在矩阵模型的基础上,提出了异龄林的三单元非线性生长模型,并分别以线性矩阵模型和非线性矩阵模型对林分的生长动态进行了预测。结果表明,非线性模型与矩阵模型的联合使用,具有结构严谨和精度高的优点,不失为一种预测林分生长动态的有效方法。文中所用材料来自长白山林区的红松(Pinus koraiensis)针阔混交林。     

Characterization of the sorption of an anthranilate fungicide in soil using thermal analytical and mineralogical techniques

The sorption of pesticides to soil particles has implications for their distribution and fate in the soil environment. A batch equilibrium technique was used to investigate sorption of the fungicide AEC623892 to intact and hydrogen-peroxide-treated whole soils and several particle-size fractions isolated from them. Sorption of AEC623892 to the soil as a whole was low. K(f oc) values measured in the whole soils were 169.2 and 41.9 ml g(-1) for Soil A and Soil B respectively. The highest values of K(f oc) were measured in soil particle-size fractions <53 microm (266.5 ml g(-1) in the 2-20 microm fraction of Soil A; 471.9 ml g(-1) in the 20-53 microm fraction of Soil B). Sorption was most irreversible in the 2-20 microm fractions. Overall, treatment of soil particle-size fractions with hydrogen peroxide resulted in lower values of K(f oc) (112.3 ml g(-1) in Soil A whole soil and 30.9 ml g(-1) in Soil B whole soil). In both soils, the maximum sorption among hydrogen-peroxide-treated samples was observed in the <2 microm fraction (166.6 and 311.0 ml g(-1) for Soil A and Soil B, respectively). Investigation of the mineralogical composition of the soils suggested that the clay mineralogy (dominated by kaolinite and illite) is less likely to account for the differences in sorption observed than differences in the characteristics of the soil organic matter. Thermal analysis of the different soil fractions indicated that hydrogen peroxide treatment preferentially removed aliphatic fractions of organic matter, but had less effect on lignin-like, aromatic fractions.     

Degradation and sorption of atrazine, hexazinone and procymidone in coastal sand aquifer media

The degradation, sorption and transport of atrazine, hexazinone and procymidone in saturated coastal sand aquifer media were investigated in batch and column experiments. The pesticides were incubated with sterilised and non-sterilised groundwater or a mixture of groundwater and the aquifer material in the dark at 15 degrees C for 120 days. The estimated half-lives of the pesticides (and their ranges) in the mixture of groundwater and aquifer sand were 36 (31-40), 54 (40-77) and 84 (46-260) days for atrazine, procymidone and hexazinone, respectively. Compared with the relevant results for the groundwater-sand mixture phase, the estimated half-life of pesticides in the groundwater phase alone was shorter for procymidone (21 days) but longer for hexazinone (134 days); atrazine was not degraded in the groundwater phase. Chemical degradation appeared to have played the predominant role in the degradation of hexazinone and procymidone in the aquifer system, while both chemical and biological processes seemed to be important for the degradation of atrazine. Batch isothermal experiments were carried out at pH 4.6-4.7 to obtain sorption coefficients under equilibrium conditions. The isothermal data of the pesticides fitted well with the non-linear Freundlich function with an exponent of sorption coefficient that was greater than one. Contrary to reports in the literature, sorption of atrazine was the greatest, and procymidone was slightly more sorbed than hexazinone. A column experiment was conducted at a typical field-flow velocity of 0.5 m day(-1) over 60 days to study pesticide attenuation and transport in flow dynamic conditions. Retardation factors, R, derived from a two-site sorption/desorption model were 8.22, 1.76 and 1.63 for atrazine, procymidone and hexazinone, respectively. Atrazine displayed the lowest mobility and the mobility of procymidone was only slightly less than that of hexazinone, which is consistent with observations in the batch experiment. A possible explanation for these observations is that ionic atrazine is bound to oppositely charged ionic oxides, and ionic oxides have less effect on the sorption of the non-ionic procymidone. The significant tailing in the pesticide breakthrough curves (BTCs) in comparison with the bromide BTC, together with model-simulated results, suggests that the transport of the pesticides was under chemical non-equilibrium conditions with R values that were less than their equivalent values predicted using the batch equilibrium isothermal data. As a result of non-linear kinetic sorption, retardation factors of the pesticides in groundwater systems would not be constant and will decrease with decreasing pesticide concentrations and increasing flow velocities. Hence, the use of equilibrium isotherm data will probably over-predict the sorption of pesticides in groundwater systems. Rhodamine WT, a commonly used groundwater tracer, was significantly retarded (R = 5.48) and its BTC was much more spread out than the bromide BTC. Therefore, it would not be a good tracer for the indication of groundwater flow velocity and dispersion for the coastal sand aquifer system. In contrast to some aquifer media, the dye tracer was unsuitable as a marker of the appearance of atrazine in a coastal sand aquifer system.     

菲在不同性质黑炭上的吸附动力学和等温线研究

在300、500和700℃3种条件下加热木屑制备得到3种黑炭,并对其结构和组成进行了表征。通过吸附动力学实验和平衡吸附实验,研究了菲在这些黑炭样品上的吸附动力学和平衡吸附,分别应用拟一阶、拟二阶和叶洛维奇3种动力学模型及Freundlich吸附等温方程对实验数据进行了拟合。结果表明,菲在黑炭样品上的吸附可以分为极快吸附、快吸附和慢吸附3个阶段,拟一阶动力学和叶洛维奇动力学方程仅能对菲在黑炭上吸附动力学的某个阶段拟合较好,而拟二阶动力学模型可较好地拟合菲的整体吸附动力学过程。说明菲在黑炭上的吸附由多个过程控制,水膜扩散、吸附剂颗粒表面扩散和吸附剂内部微孔扩散等多个过程导致了其吸附动力学的复杂性。在快吸附阶段,菲在各个黑炭上吸附动力学的差异,主要受黑炭疏水性影响。Freundlich模型对吸附等温数据的拟合结果进一步证实,多环芳烃菲在黑炭样品上的吸附受多种机制影响。     

Approach to Determine Value of Variable Vapor Permeability of Autoclaved Aerated Concrete

The sorption isotherms and vapor permeability of autoclaved aerated concrete are obtained with the static gravimetric method and the cup method at 15℃, 25℃ and 35℃, respectively. The approaoh to determine value of variable permeability has been discussed. Meanwhile, it has been compared with the fixed value in Thermal Design Code for Civil Building (GB 50176-93). The results show that temperature dependence of the sorption isotherms and vapor permeability of autoclaved aerated concrete is small within test temperature range. Moreover, for adsorption process in medium or whole RH range, the average permeability obtained from our method is almost the same as that in the Code. This method can be extended to other porous building materials to obtain accurate permeability throughout whole RH range for both adsorption and desorption processes.     

冷却剂参数对铣槽喷管低周疲劳寿命的影响

采用有限体积流固耦合计算方法、非线性有限元热结构耦合分析方法和局部应变法研究大面积比铣槽喷管三维再生冷却槽道在循环工作条件下的热结构变形与低周疲劳寿命,并对比分析了冷却剂质量流量与入口温度对铣槽喷管疲劳使用寿命的影响。计算结果表明,铣槽喷管热结构响应呈现复杂的三维效应,应变较大位置主要分布在与肋连接的内衬区域,喷管中部的残余应变量最大;冷却槽道低周疲劳寿命分布和热结构响应基本一致,最小寿命位于喷管中部与肋相连的内衬区域燃气侧;随冷却剂质量流量增加,铣槽喷管低周疲劳寿命不断提高;随冷却剂入口温度增加喷管尾部低周疲劳寿命值不断降低,而喷管中前部的低周疲劳寿命值却不断提高,当冷却剂入口温度为280K左右时,本文的铣槽喷管总体使用寿命达到最大。      

Effects of Organic Matter-Rich Amendments on Selenium Mobility in Soils

Soil organic matter (SOM) plays an important role in the Se dynamics in soil. The potential effects of vermicompost and digestate as important sources of SOM on selenium (Se) mobility were assessed in this study. Three soils differing in their physicochemical parameters, fluvisol, chernozem, and luvisol, were chosen, and three types of vermicomposts based on various bio-waste materials as digestate (vermicompost 1), kitchen waste with woodchips (vermicompost 2), and garden bio-waste (vermicompost 3) were used due to their high organic matter content. Additionally, digestate samples alone were applied. To evaluate the potential effect of vermicompost application on sorption characteristics of soils, batch sorption experiments were performed. The results showed a predominant effect on Se species in the soils, where selenite sorbed more intensively compared to selenate, regardless of the soil and ameliorative material applied. In the control, the soil sorption ability of selenite tended to decrease in the order:fluvisol > luvisol > chernozem. However, these differences were not significant. Moreover, the effects of the ameliorative materials depended on both soil and amendment used. In fluvisol, all the amendment applications resulted in a decrease in distribution coefficient (K_d values) of Se, whereas in chernozem, this effect was observed only for the digestate-based vermicompost 1. Increasing K_d levels were reported in luvisol treated with digestate; the application of garden bio-waste-based vermicompost 3 tended to decrease the K_d values. Further studies are required on long-term effects of these amendments on Se mobility in soils and the role of individual organic matter fractions in this context.     

Physical carbon‐sequestration mechanisms under special consideration of soil wettability

The protective impact of aggregation on microbial degradation through separation has been described frequently, especially for biotically formed aggregates. However, to date little information exists on the effects of organic‐matter (OM) quantity and OM quality on physical protection, i.e., reduced degradability by microorganisms caused by physical factors. In the present paper, we hypothesize that soil wettability, which is significantly influenced by OM, may act as a key factor for OM stabilization as it controls the microbial accessibility for water, nutrients, and oxygen in three‐phase systems like soil. Based on this hypothesis, the first objective is to evaluate new findings on the organization of organo‐mineral complexes at the nanoscale as one of the processes creating water‐repellent coatings on mineral surfaces. The second objective is to quantify the degree of alteration of coated surfaces with regard to water repellence. We introduce a recently developed trial that combines FTIR spectra with contact‐angle data as the link between chemical composition of OM and the physical wetting behavior of soil particles. In addition to characterizing the wetting properties of OM coatings, we discuss the implications of water‐repellent surfaces for different physical protection mechanisms of OM. For typical minerals, the OM loading on mineral surfaces is patchy, whereas OM forms nanoscaled micro‐aggregates together with metal oxides and hydroxides and with layered clay minerals. Such small aggregates may efficiently stabilize OM against microbial decomposition. However, despite the patchy structure of OM coating, we observed a relation between the chemical composition of OM and wettability. A higher hydrophobicity of the OM appears to stabilize the organic C in soil, either caused by a specific reduced biodegradability of OM or indirectly caused by increased aggregate stability. In partly saturated nonaggregated soil, the specific distribution of the pore water appears to further affect the mineralization of OM as a function of wettability. We conclude that the wettability of OM, quantified by the contact angle, links the chemical structure of OM with a bundle of physical soil properties and that reduced wettability results in the stabilization of OM in soils.