有机酸对珠江三角洲水稻土镉解吸行为的影响

用批平衡实验方法,研究了3种有机酸及其两两混合酸在一系列pH值梯度下(pH3~7)对珠江三角洲沉积型水稻土镉(Cd)解吸的影响.结果表明,只有柠檬酸及含柠檬酸的混合酸在较低酸度区(pH>5)可以显著促进Cd的解吸,这一效应与浓度成正相关,而苹果酸、草酸及二者的混合酸在所试验酸度范围均促进了Cd吸附,特别是草酸,促进作用随浓度的升高而增强.在较低pH区(pH<5),苹果酸最有利于Cd解吸,在高pH区(pH≥5),柠檬酸最有利于Cd解吸,草酸的Cd解吸能力最低.混合有机酸交互作用不显著,对Cd解吸的影响约等于各个单独酸的作用之和,但在一些酸度条件下,可存在颉颃作用.图3表2参22     

Effect of low molecular weight organic acids on adsorption and desorption of fluoride on variable charge soils

The effect of four low molecular weight organic acids on F⁻ adsorption by two variable charge soils was investigated using a batch method. The organic acids reduced F⁻ adsorption through competition by the acids with F⁻ for sorption sites. Oxalic and malonic acids, both of which have simpler chemical structures, were more effective than citric or malic acid. The effect of organic acids on F⁻ adsorption was more prominent at higher pH values and with larger amounts of the organic acids. The desorption study showed that the organic acids enhanced the desorption of F⁻ adsorbed by the soils. In the control and malic acid systems, desorption increased sharply with decreasing pH, while in the oxalic acid system, desorption rose slightly with decreasing pH. Desorption also increased with increasing amount of organic acid added. There are two possible mechanisms for the effect of the organic acids on F⁻ adsorption and desorption: (1)␣competition of the organic acids with F⁻ for adsorption sites and (2) dissolution of the adsorbents, especially dissolution of soil Al.     

淹水还原作用下土壤镉的吸附与解吸特征的初步探讨

利用黄棕壤发育的水稻土(pH6.53),设置6个不同处理恒温(25±0.1)℃培养20d,初步探讨了3种还原强度土壤对Cd的吸附和解吸特征。试验数据显示:强度还原土壤,Eh和pH降低并稳定在-474mV和5.02水平,Cd吸附率由开始时的99.96%下降到94.70%,Cd解吸率平均为90.01%;中度还原土壤,Eh下降至-90mV左右,pH略有上升,Cd吸附率和解吸率平均分别为99.96%和66.09%;氧化态土壤的Eh、pH和Cd解吸率变化都比较小,平均分别为400.4mV、6.11和46.78%。此结果表明,处于不同还原状况下的土壤表面对Cd吸附和解吸有所差别;强度还原土壤对外源Cd的吸附率小于中度还原土壤对外源Cd的吸附率;土壤吸附外源Cd的解吸率,由大到小的次序依次为强度还原土壤,中度还原土壤,氧化状态土壤;还原程度越强,土壤对Cd的吸附率越低,Cd的解吸率也越高;还原条件下土壤Eh、pH、交换性亚铁和水溶性有机质含量是影响土壤Cd吸附和解吸的主要因素。     

低分子量有机酸对可变电荷土壤吸附铝的影响机制

通过吸附性铝的解吸实验研究了低分子量有机酸对三种可变电荷土壤(2种砖红壤和1种赤红壤)吸附铝的影响机制，结果表明，柠檬酸、苹果酸和酒石酸等带有3个及3个以上活性官能团的有机酸在低pH条件下可以通过形成土壤一有机酸一铝三元表面络合物和增加土壤的表面负电荷两种机制显著增加土壤对铝离子的吸附量，但以前一种影响机制为主。乳酸、水杨酸、草酸和丙二酸等带有2个活性官能团的有机酸仅通过改变土壤的表面负电荷影响铝的吸附。土壤氧化铁是土壤吸附有机酸的主要载体，当用化学方法将土壤中的氧化铁除去后，有机酸对铝吸附的影响变小。在pH5．0时有机酸主要通过形成可溶性有机铝络合物减小土壤对铝的吸附，但有机酸的存在增加了Al^3 在吸附性铝中所占的比例，导致铝的解吸率增加。土壤中大量氧化铁的存在使其即使在低pH下也能对铝离子发生专性吸附，导致吸附性铝的解吸率减小。     

Washing out heavy metals from contaminated soils from an iron and steel smelting site

Washing is a promising method for separating contaminants bound to the particles of soil ex-situ by chemical mobilization. Laboratory batch washing experiments were conducted using deionized water and varying concentrations of oxalic acid, citric acid, tartaric acid, acetic acid, hydrochloric acid and ethylenediaminetetra acetic acid (EDTA) to assess the efficiency of using these chemicals as washing agents and to clean up heavy metals from two heavily polluted soils from an iron and streel smelting site. The toxicity reduction index and remediation costs were analyzed, and the results showed that the soils were polluted with Cd, Pb and Zn. Hydrochloric acid and EDTA were more efficient than the other washing agents in the remediation of the test soils. The maximum total toxicity reduction index showed that 0.5 mol·L^-1 hydrochloric acid could achieve the remediation with the lowest costs.     

Retention of 137cesium in acid sulphate soils of South Central Thailand

Adsorption and desorption of ¹³⁷Cs by acid sulphate soils from the Nakhon Nayok province, South Central Plain of Thailand located near the Ongkarak Nuclear Research Center (ONRC) were investigated using a batch equilibration technique. The influence of added limestone (12 and 18 tons ha^-1) on ¹³⁷Cs adsorption-desorption was studied. Based on Freundlich isotherms, both adsorption and desorption of ¹³⁷Cs were nonlinear. A large portion (98.26-99.97%) of added ¹³⁷Cs (3.7 × 10³-7.03 × 10⁵ Bq l^-1) was sorbed by the soils with or without added lime. The higher lime treatments, however, favoured stronger adsorption of ¹³⁷Cs as compared with soil with no lime, which was supported by higher K_ads values. The addition of lime, the cation exchange capacity and pH of the soil increased and hence favoured the stronger adsorption of ¹³⁷Cs. Acid sulphate soils with a high clay content, medium to high organic matter, high CEC, and predominant clay types consisting of a mixture of illite, kaolinite, and montmorillonite were the main soil factors contributing to the high ¹³⁷Cs adsorption capacity. Competing cations such as NH₄⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺ had little influence on ¹³⁷Cs adsorption as compared with liming, where a significant positive correlation between K_ads and soil pH was observed. The ¹³⁷Cs adsorption-desorption characteristics of the acid sulphate soils studied exhibited a very strong irreversible sorption pattern. Only a small portion (0.09-0.58%) of ¹³⁷Cs adsorbed at the highest added initial ¹³⁷Cs concentration was desorbed by four successive soil extractions. Results clearly demonstrated that Nakhon Nayok province acid sulphate soils have a high ¹³⁷Cs adsorption capacity, which limits the ¹³⁷Cs bioavailability.     

生物炭对土壤中阿特拉津吸附特征的影响

为探究生物炭对土壤中阿特拉津的吸附特征及影响因素,采用批处理实验研究了灭菌(T1)、5%秸秆生物炭+灭菌(T2)、未灭菌(T3)和5%秸秆生物炭+未灭菌(T4)条件下对土壤中阿特拉津吸附特征及土壤理化性质的影响.结果表明,在最初0—12 h内,不同处理下阿特拉津吸附量均随时间的延长而快速增加,而在12—96 h内增加较为缓慢并逐渐趋于平衡.在96 h时,T2和T4处理下阿特拉津最大吸附量分别达到46.22 mg·kg^-1和46.43 mg·kg^-1,而未添加生物炭的T1和T3处理则有所降低,分别为44.20 mg·kg^-1和43.09 mg·kg^-1.准二级动力学模型更好地拟合不同处理下土壤对阿特拉津吸附特征,T2和T4处理下吸附速率常数K分别为0.257 kg·mg^-1·h^-1和0.339 kg·mg^-1·h^-1,显著高于未添加生物炭处理的T1和T3处理(K分别为-0.083 kg·mg^-1·h^-1和-0.261 kg·mg^-1·h^-1).内扩散模型显示添加生物炭后,土壤对阿特拉津的吸附是一个由边界扩散、内部孔隙扩散等多因素控制的复杂化学过程.添加生物炭可显著提高土壤pH、有机碳、碱解氮、速效磷和速效钾含量,其中土壤有机碳含量与阿特拉津最大吸附量之间存在显著的正相关关系(P<0.05).由此可见,添加生物炭可以提高土壤对阿特拉津的固持能力,减少其淋溶迁移风险,从而达到修复阿特拉津污染土壤的目的.     

Adsorption and desorption of steroid hormones on saline soil

● Organic matter content significantly affected adsorption of E2/EE2 on saline soil. ● EE2 possessed higher competition intensity for adsorption sites than E2. ● The adsorption of E2/EE2 on saline soil was a spontaneous exothermic process. ● Desorption capacity of EE2/E2 accounted for 40%/78% of the total adsorption capacity. Soil organic matter content was the main driving factor affecting adsorption and desorption process of 17β-estradiol (E2) and 17α-ethynylestradiol (EE2) on saline soil. The adsorption and desorption of E2 and EE2 on three saline soils showed the similar behavior that soil with the highest organic content possessed the highest adsorption capacity and the lowest desorption capacity for E2 and EE2. The adsorption capacity of untreated soil samples (with organic matter) was larger than that of soil samples without organic matter. For soil with the largest adsorption capacity, adsorption capacity of E2/EE2 on the untreated soil and soil colloid (with organic matter) respectively reached 0.15/0.30 μg/g and 0.16/0.33 μg/g while the soil and soil colloid without organic matter hardly adsorbed pollutants. The adsorption capacity of E2/EE2 at the initial concentration of 100 μg/L was 25/15 times higher than that at the initial concentration of 5 μg/L. E2 and EE2 had the same adsorption sites on saline soil while EE2 possessed higher competition intensity for adsorption sites than E2. Pseudo-first-order model (R² = 0.995–0.986) and Langmuir model (R² = 0.989–0.999) could better fit the adsorption process of E2 or EE2. The thermodynamic study further showed that the adsorption of E2/EE2 on saline soil was a spontaneous exothermic process. The desorption capacity of EE2/E2 accounted for 40%/78% of the total adsorption capacity to possibly exert potential risk to the groundwater. The variation of the salinity led to the variation of soil organic carbon which subsequently changed the adsorption and desorption behaviors of endocrine disrupting chemicals in coastal saline soil. This study provides a new insight on the interfacial behavior of endocrine disrupting chemicals on saline soil.     

环丙沙星在亚高山草甸不同深度土壤上的吸附及其影响因素

兽用抗菌药物环丙沙星(CIP,ciprofloxacin)的大量使用引发了人们的广泛关注.文章研究了CIP在亚高山草甸土剖面土壤上的吸附动力学、吸附热力学和pH、有机质含量、阳离子交换量等因素对吸附的影响,以揭示CIP在亚高山草甸土上的吸附机制,为CIP的生态风险评价提供一定的依据.结果表明,CIP在亚高山草甸土上的吸...     

Characterization of soil low-molecular-weight organic acids in the Karst rocky desertification region of Guizhou Province, China

Soil low-molecular-weight (LMW) organic acids play important roles in the soil-forming process and the cycling of nutrients in Karst regions. In this study, we quantified the contents of LMW organic acids (including lactate, acetate, formate, malate, and oxalate) in soil solution over the Karst region of Guizhou Province, China using ion chromatography. The concentration of total LMW organic acids in topsoil solution ranged from 0.358 to 1.823 μmol·g^-1, with an average of 0.912 μmol·g^-1. The mean concentrations of lactate, acetate, formate, malate, and oxalate were 0.212±0.089, 0.302±0.228, 0.301±0.214, 0.014±0.018 and 0.086±0.118 μmol·g^-1, respectively. There were also significant difference in the contents of these acids among four phases of rocky desertification, and their concentrations decreased with the aggravation of rocky desertification. The concentrations of the LMW organic acids were significantly positive correlated each other. Significant positive correlations were also observed among individual LMW organic acids in soil solution, and between them and soil available P, available K, exchangeable Ca, respectively. Furthermore, the concentrations of LMW organic acids were significantly positively correlated with inorganic anions (chlorides, nitrates, and sulfates) in Karst topsoil solution. Therefore, the concentrations of soil LMW organic acids might be one of driving force in the Karst rock desertification process in Guizhou Province.     

长三角和珠三角农业土壤对Pb、Cu、Cd的吸附解吸特性

研究了长江三角州和珠江三角州10种代表性农业土壤对重金属Pb、Cu和Cd的吸附与解吸特性。结果表明:大多数土壤对重金属有较强吸附能力,土壤性质对重金属吸附与解吸行为有很大影响。其中,pH值是影响土壤对重金属吸附与解吸的最重要因素,土壤重金属吸附量随pH值增加而增加。土壤pH值和有机质或粘粒含量较高的土壤(如乌栅土、青紫泥田、黄斑田),其对重金属吸附能力高于pH值和有机质或粘粒含量较低的土壤(如黄筋泥、粉泥田)。重金属解吸量随重金属吸附量和土壤重金属饱和度增加呈指数增加趋势;土壤对重金属的吸附能力从强至弱依次为Pb、Cu、Cd;当3种重金属共存时,重金属之间竞争能力强弱顺序与吸附能力顺序相同。重金属之间竞争作用随土壤酸度和重金属污染程度的增加而增强。     

Whole pictures of halogenated disinfection byproducts in tap water from China’s cities

When bromide/iodide is present in source water, hypobromous acid/hypoiodous acid will be formed with addition of chlorine, chloramine, or other disinfectants. Hypobromous acid/hypoiodous acid undergoes reactions with natural organic matter in source water to form numerous brominated/iodinated disinfection byproducts (DBPs). In this study, tap water samples were collected from eight cities in China. With the aid of electrospray ionization-triple quadrupole mass spectrometry by setting precursor ion scans of m/z 35, m/z 81, and m/z 126.9, whole pictures of polar chlorinated, brominated, and iodinated DBPs in the tap water samples were revealed for the first time. Numerous polar halogenated DBPs were detected, including haloacetic acids, newly identified halogenated phenols, and many new/unknown halogenated compounds. Total organic chlorine, total organic bromine, and total organic iodine were also measured to indicate the total levels of all chlorinated, brominated, and iodinated DBPs in the tap water samples. The total organic chlorine concentrations ranged from 26.8 to 194.0 μg·L^–1 as Cl, with an average of 109.2 μg·L^–1 as Cl; the total organic bromine concentrations ranged from below detection limit to 113.3 μg·L^–1 as Br, with an average of 34.7 μg·L^–1 as Br; the total organic iodine concentrations ranged from below detection limit to 16.4 μg·L^–1 as I, with an average of 9.1 μg·L^–1 as I; the total organic halogen concentrations ranged from 31.3 to 220.4 μg·L^–1 as Cl, with an average of 127.2 μg·L^–1 as Cl.     

预浓缩/柱箱制冷GCMS/FID法测定大气中117种挥发性有机物

建立了罐采样、吸附剂辅助电子制冷预浓缩-柱箱制冷GCMS/FID同时测定大气中117种挥发性有机物(VOCs)的方法.样品经填充吸附剂的电子制冷预浓缩系统除水、除CO2、浓缩和热脱附后,采用柱箱制冷及GCMS/FID的多维切割单元,将5种C2-C3组分切到二维色谱柱进行分离并进入FID检测,甲醛及其他111种VOCs组...     

Effects of rape straw and red mud on extractability and bioavailability of cadmium in a calcareous soil

Screening of cost-effective soil amendments is important to develop “in situ” remediation techniques for cadmium (Cd) contaminated soils. In this study, different soil amendments, including red mud, a by-product of the alumina industry, and acid-treated, nano-treated by nano-particle milling, nano and acid-treated red muds, zeolite, corn straw, and rape straw, were evaluated to immobilize Cd in two added levels (2 and 5 mg Cd·kg^-1 soil) in a calcareous soil by single and sequential extractions and by cucumber (Cucumis sativus L.) pot experiments. Results indicated that cruciferous rape straw significantly decreased the concentrations of water soluble, extractable Cd in soils, and Cd in cucumber plants, and it was more effective than gramineous corn straw. Also, red mud generally decreased the extractability and bioavailability of Cd added to calcareous soils more effectively than zeolite. Furthermore, the efficiency of red mud could be increased by the treatment of nano-particle milling due to the increase in specific surface area of red mud. It is potential to use rape straw and red mud as soil amendments to develop a cost-effective and efficient “in situ” remediation technology for Cd mildly contaminated calcareous soils.     

不同部位梧桐生物质炭对水溶液中镉吸附的机理

为了探究梧桐不同部位废弃物所制备的生物质炭(皮、枝、叶)对Cd²⁺的吸附效率和稳定修复的机理,以此为园林废弃物炭化利用在重金属污染修复方面的应用提供科学依据.利用实验室模拟法,通过高温煅烧法制备梧桐不同部位生物质炭,采用元素分析仪、比表面积及孔隙分析(BET)、X射线衍射仪(XRD)、扫描电镜/能谱(SEM/EDS)及衰减全反射红外光谱(ATR-IR)等技术研究不同反应时间、重金属浓度和溶液初始pH条件下生物质炭对Cd²⁺吸附效果的影响,并运用四步萃取法和脱附实验分析生物质炭上Cd²⁺的吸附形态和稳定性.3种生物质炭都在8 h左右达到吸附平衡,最终吸附量依次为树皮炭>枝条炭>叶片炭;溶液初始浓度为0.5—2 g·L^-1时Cd²⁺的吸附量呈增长趋势,在2.5—3g·L^-1时逐渐平缓;生物质炭Cd²⁺吸附量均随着pH的升高而升高,但在pH值为5—8时,吸附的趋势逐渐平稳;树皮炭的酸溶态和非生物利用态的稳定Cd形态要高于枝条炭和叶片炭;比表面积不是影响梧桐生物质炭吸附Cd²⁺的主要影响因素,吸附动力学,ATR,XRD和重金属形态萃取均证实Cd碳酸盐类矿物生成是主导吸附机理;3种生物质炭的脱附量在4 h后逐渐趋于平衡,其中脱附量最大为叶片炭,最小为树皮炭.梧桐不同部位的初始性质对生物质炭吸附Cd²⁺具有明显的影响,其中梧桐皮具备更高的吸附量和重金属稳定形态,并且相比其他种类生物质炭有明显优势.因此,从吸附效果和生产成本的角度,本研究建议以梧桐皮为主,枝条和叶片为辅的生物质炭对重金属Cd进行修复治理.     

Zn和Cd胁迫作用对长梗白菜形态和生理性能的生态毒理影响

本文以不同Cd、Zn浓度胁迫下的长梗白菜为研究对象,采用盆栽实验,分析了Cd和Zn胁迫下长梗白菜形态参数(重量、长度、表面积、叶的分形维数)、生理性能的影响以及从土壤中提取Cd和Zn的能力.结果 表明,Cd、Zn胁迫对长梗白菜的生长具有"低促高抑"效应,且共同胁迫对生长的影响大于单一胁迫.在0.6 mg·kg-1 Cd...     

低分子有机酸对土壤氟吸附的影响

用等温平衡吸附法研究了柠檬酸、草酸对砂姜黑土和潮土氟吸附的影响 ,提出了有机酸影响氟吸附的可能机理。实验结果表明 ,有机酸对土壤氟吸附有较大的影响 :(1)当有机酸处于低浓度时 ,土壤氟吸附量随浓度升高而增加 ;高浓度时 ,土壤氟吸附量随有机酸浓度升高而降低 ;(2 )在有机酸存在条件下 ,土壤氟的吸附量与平衡氟浓度间呈极显著的直线正相关或负相关     

Optimization of thermophilic anaerobic-aerobic treatment system for Palm Oil Mill Effluent (POME)

Optimization of an integrated anaerobic-aerobic bioreactor (IAAB) treatment system for the reduction of organic matter (Chemical Oxygen Demand (COD), Biochemical Oxygen Demand (BOD) and Total Suspended Solids (TSS) concentrations) in Palm Oil Mill Effluent (POME) to legal standards with high methane yield was performed for the first time under thermophilic condition (50°C–55°C) by using response surface methodology (RSM). The experiments were conducted based on a central composite rotatable design (CCRD) with three independent operating variables, organic loading rates in anaerobic compartment (OLR_an) and mixed liquor volatile suspended solids (MLVSS) concentration in anaerobic (MLVSS_an) and aerobic compartments (MLVSS_a). The optimum conditions for the POME treatment were determined as OLR_an of 15.6 g COD·L^-1·d^-1, MLVSS_an of 43100 mg·L^-1, and MLVSS_a of 18600 mg·L^-1, where high aerobic COD, BOD and TSS removal efficiencies of 96.3%, 97.9%, and 98.5% were achieved with treated BOD of 56 mg·L^-1 and TSS of 28 mg·L^-1 meeting the discharge standard. This optimization study successfully achieved a reduction of 42% in the BOD concentrations of the final treated effluent at a 48% higher OLR_an as compared to the previous works. Besides, thermophilic IAAB system scores better feasibility and higher effectiveness as compared to the optimized mesophilic system. This is due to its higher ability to handle high OLR with higher overall treatment efficiencies (more than 99.6%), methane yield (0.31 L CH₄·g^-1 COD_removed) and purity of methane (67.5%). Hence, these advantages ascertain the applicability of thermophilic IAAB in the POME treatment or even in other high-strength wastewaters treatment.     

铁基生物炭钝化Cd大田试验研究

近年来,稻田Cd污染引起的环境及健康问题日益突出。应用钝化技术对土壤中有效性Cd进行钝化对稻田生态系统中Cd的生物地球化学循环具有重要的理论和实际意义。在广东省韶关市仁化县董塘镇红星村一受Cd污染的稻田上,设置大田试验,研究铁基生物炭对Cd在大田土壤-水稻系统迁移的影响以及对作物产量的影响。试验共设6个处理:(1)空白对照;(2)每一季水稻插秧前,一次性施加1500 kg·hm^-2的普通生物炭;(3)每一季水稻插秧前,一次性施加75 kg·hm^-2的零价铁(Fe0);(4)每一季水稻插秧前,一次性施加1500 kg·hm^-2、ω(Fe)=1%的铁基生物炭(ω(Fe)=1%in Fe-Biochar);(5)每一季水稻插秧前,一次性施加1500 kg·hm^-2、ω(Fe)=3%的铁基生物炭(ω(Fe)=3%in Fe-Biochar);(6)每一季水稻插秧前,一次性施加1500 kg·hm^-2、ω(Fe)=5%的铁基生物炭(ω(Fe)=5%in Fe-Biochar)。结果表明:(1)施用生物炭、铁粉和铁基生物炭土壤钝化调理剂可以增加水稻产量,显著降低籽粒重金属Cd含量;(2)施用铁基生物炭可以显著增加水稻根表铁膜Fe含量,同时显著增加水稻根表铁膜固定的Cd量,抑制重金属Cd向籽粒的运输累积。综合考虑施用成本和钝化效果,对于Cd污染稻田,建议施用1500 kg·hm^-2、ω(Fe)=3%的铁基生物炭材料。     

Removal of Cr(VI) from aqueous solution using waste weed, Salvinia cucullata

Biosorption studies of Cr(VI) were carried out using waste weed, Salvinia cucullata. Various adsorption parameters were studied, such as agitation speed, contact time, pH, particle size, and concentrations of adsorbent and adsorbate. The equilibrium was achieved in 12 h. A lower pH favoured adsorption of Cr(VI). The kinetics followed pseudo-second-order rate equations. The adsorption isotherm obeyed both the Langmuir and Freundlich models. The calculated activation energy (1.1 kJ mol^-1) suggested that the adsorption followed a diffusion-controlled mechanism. Various thermodynamic parameters such as Δ G^°, Δ H^°, and Δ S^° were also calculated. The positive values of enthalpy indicated the endothermic nature of the reaction, and Δ S^° showed the increasing randomness at the solid liquid interface of Cr(VI) on the adsorbent, which revealed the ease of adsorption reaction. These thermo-dynamic parameters showed the spontaneity of the reaction. The maximum adsorption of uptake (232 mg g^-1) compared well with reported values of similar adsorbents. The rate-determining step was observed to follow an intra-particle diffusion model.