Effects of pH, organic acids, and inorganic ions on lead desorption from soils

The desorption characteristics of lead in two variable charge soils (one developed from Arenaceous rock (RAR) and the other derived from Quaternary red earths (REQ)) were studied, and the effects of pH value, organic acid, and competitive ions were examined. Desorption of Pb(2+) decreased from nearly 100.0 to 20.0% within pH 1.0-4.0 in both soils, and then the decrease diminished at pH > 4.0. Organic ligands at relatively low concentrations (< or =10(-3) mol L(-1)) slightly inhibited Pb(2+) desorption, but enhanced Pb(2+) desorption at higher concentrations. In this study, citric acid or acetic acid at higher concentrations (>10(-3) mol L(-1)) had the greatest improvement of Pb(2+) desorption, followed by malic acid; and the smallest was oxalic acid. Desorption of the adsorbed Pb(2+) increased greatly with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Pb(2+) desorption more than Zn(2+) at the same loading.     

Effects of low-molecular-weight organic acids and residence time on desorption of Cu, Cd, and Pb from soils

Effects of low-molecular-weight organic acids (LMWOAs) and residence time on desorption of Cu, Cd, and Pb from two typical Chinese soils were studied. Citric, malic, and acetic acids were chosen as representatives of LMWOAs commonly present in soils. CaCl(2) and NaNO(3) were used in desorption as they were main soil background electrolytes for comparison. Desorption of Cu, Cd, and Pb from both soils followed the descending order: citric acid>malic acid>acetic acid>CaCl(2)>NaNO(3), which was consistent with the order of stability of Cu-, Cd-, and Pb-LMWOAs complexes from large to small and ion exchange ability of Ca(2+) and Na(+). Desorption of metals by inorganic salts decreased with increasing desorption solution pH. Whereas desorption of metals by LMWOAs showed different trend in response to pH change due to their different complexing abilities. Malic and acetic acids released less metals at low pH 3.1 compared with citric acid at pH 7, indicating that pH was not the dominant factor governing the release of metals. In addition, all LMWOAs desorbed more metals than inorganic salts, CaCl(2) and NaNO(3). Therefore, organic ligands played a dominant role in desorption of heavy metals. More metals were released from Jiangxi soil than from Heilongjiang soil due to lower soil pH, CEC, organic matter content and manganese oxide of Jiangxi soil. Generally, desorption of metals decreased with increasing residence time of metals in soils.     

氯盐对含汞土壤热脱附的影响

采用管式电阻炉对不同氯盐调理的含汞土壤进行热脱附实验,研究氯盐种类和炉温等对汞脱除效果的影响,分别从汞脱除率、热重测试和XRD汞形态分析3个方面进行评价。结果表明,不同温度下添加氯盐均对汞脱除率有明显提升。230℃时,添加氯化铁、氯化镁和氯化钙调理相比对照组(不添加氯盐),汞脱除率分别提升66.2%、49.3%和15.8%,即促进效果:FeCl3>MgCl2>CaCl2。在300℃下加热25 min时,添加氯化铁调理的汞脱除率为96.1~96.2%,与对照组相比,最高提升了68.3%。热重测试结果显示,载气对汞的挥发影响较小,湿法投加氯盐效果比干法投加更明显。炉尾晶体XRD分析结果表明,在低温条件下氯盐促进样品中汞向氯化汞转变从而提高了汞脱除率。添加氯盐调理提高了汞脱除率,同时缩短了汞热脱附达到稳定的时间。     

Effect of fluoride on pH, organic matter and solubility of elements in soils

The effect of NaF addition on pH, organic matter and the solubilities of fifteen elements was investigated on twenty-eight surface soil samples. Four concentrations of NaF were added: 0, 10(-2.7), 10(-1.7) and 10(-1.0)m F in solution. Addition of NaF increased the pH and the solubility of organic matter for all soils. The magnitude of these increases was higher for acid than for alkaline soils. Aluminum, Fe and Ca showed the greatest increases in solubility while Mg, K, Mn and P showed intermediate increases. The elements Cd, Cr, Ni, Cu, Zn, B, Mo and Ba showed only slight increases in solubility. Another experiment was conducted to test whether the effects of NaF on pH, organic matter and the solubilities of various elements were due to F or Na. Four levels of NaCl similar to those for NaF were added to three acid and two alkaline soils. The results confirmed the effects of F on soil pH, organic matter and the solubilities of all elements investigated except those of K, Ca and Mg. Addition of Na as NaF resulted in release of K, Ca and Mg from the exchange sites on solid surfaces into solution.     

有机质对污染土壤中DDTs热脱附行为的影响

采用2种不同性质土壤(黑土和棕壤)作为供试土壤,利用DDT农药自配滴滴涕类(DDTs,包括p,p'-DDT、o,p'-DDT、p,p'-DDD、p,p'-DDE)污染土壤.采用热脱附方法,研究了原土及去有机质后土壤中DDTs在300℃,6个停留时间(5、10、20、30、40和50 min)下的去除率以及脱附后土壤中D...     

Effect of organic acids on adsorption and desorption of rare earth elements

Effect of citric, malic, tartaric and acetic acids on adsorption of La, Ce, Pr and Nd by and desorption from four typical Chinese soils was studied. Generally, adsorption capacities of rare earth elements (REEs) were significantly correlated with the cation exchange capacity (CEC) of soils. In the presence of acetic acids adsorption of REEs was similar to that in the presence of Ca(NO3)2. However, in the presence of citric, malic and tartaric acids adsorption of REEs by Heilongjiang, Zhejiang and Guangdong soils decreased to varying extents if compared with that in the presence of nitrate and acetic acid. The significance of suppression followed the order of citric acid > malic acid > tartaric acid > acetic acid, which was consistent with the order of stability of complexes of REEs with these organic acids. However, the adsorption increased with increasing equilibrium solution pH. For Jiangxi soil with low soil pH, CEC and organic matter these organic acids exerted an even more serious suppression effect on the adsorption of REEs. Another feature of the relationship between the adsorption of REEs and equilibrium solution pH was that the adsorption of REEs decreased with increase of pH from 2 to 4.5 and then slightly increased with further increase of pH. Desorption of REEs varied with soils and with organic acids as well. REEs were released easily from Heilongjiang, Zhejiang and Guangdong soils in the presence of organic acid. Generally, desorption of REEs decreased with increasing equilibrium solution pH. Effect of organic acids on desorption of REEs from Jiangxi soil was more complicated. In the presence of citric and malic acids no decrement and/or slight increase in desorption of REEs were observed over the equilibrium solution pH from 3 to 6.5. The reasons for this were ascribed to the strong complexing capacity of citric and malic acids and low soil pH, CEC and organic matter of Jiangxi soil.     

Transformations of elemental mercury to inorganic and organic forms in mercury and hydrocarbon co-contaminated soils.

There are many industrial sites, such as gas processing plants, that are contaminated with both mercury and hydrocarbons. These sites tend to be localized but can have very high concentrations of mercury in the soil and heterogeneous distribution of hydrocarbons. The original form of mercury in many cases was elemental mercury from broken manometers. Over time the mercury has become redistributed within soil and has undergone chemical transformations into new forms. The forms of mercury will govern the chemical behavior and the availability of the mercury to biological receptors. The availability of the mercury is important as it will govern the risk associated with the contaminated soil and will also determine the effectiveness of any attempts at remediation. In the present study a chemical extraction protocol was used to determine the forms of mercury in soil originally contaminated by spillage of elemental mercury and petroleum hydrocarbons. Chemical extractions have been used in the past to determine the forms of mercury in uncontaminated soils and several researchers have used them to study contaminated soils. However, to date, no researchers have studied the forms of mercury in soils following years of weathering of elemental mercury after a spill. This study shows that decades after the original spill the elemental mercury has transformed and is dominantly (up to 85%) associated with soil organic matter, and to a lesser extent the mineral fraction of soil.     

Cadmium adsorption and desorption behaviour on goethite at low equilibrium concentrations: effects of pH and index cations

The transport and bioavailability of cadmium is governed mainly by its adsorption-desorption reactions with minerals such as goethite--a common iron oxide mineral in variable charged and highly weathered tropical soils. Soil factors such as pH, temperature, solution Cd concentration, ionic strength and ageing affect Cd adsorption on goethite. The desorption behaviour of Cd from goethite at low concentrations is not fully understood. This study investigates the adsorption-desorption of Cd at low Cd concentrations (Cd adsorbed on goethite from 20 to 300 microM Cd solutions) in Na and Ca nitrate solutions of 0.03 M nominal ionic strengths. Synthetic goethite prepared by ageing a ferric hydroxide gel at high pH and room temperature was used for Cd adsorption and desorption studies. For desorption experiment 10 successive desorptions were made for the whole range of initial Cd concentrations (20-300 microM) in the presence of 0.01 M Ca(NO3)2 or 0.03 M NaNO3 solutions. Cadmium adsorption was found to be higher in Na+ than Ca2+ probably due to the competition of Ca2+ ions with Cd2+ ions for adsorption sites on the surfaces of goethite. The effect of index cation on Cd adsorption diminished with increase in pH from 5.0 to 6.0. Cadmium desorption decreased with increase in pH from 5.0 to 6.0 in both Na and Ca systems. After 10 successive desorptions with 0.03 M NaNO3 at the lowest initially adsorbed Cd approximately 45%, 20% and 7% of the adsorbed Cd was desorbed at pH 5.0, 5.5 and 6.0, respectively. The corresponding desorptions in the presence of 0.01 M Ca(NO3)2 were 49%, 22% and 8%, respectively. The Freundlich parameter, k, based on each progressive step of desorption at different adsorbed concentration increased with increasing desorption step, which may indicates that a fraction of Cd was resistant to desorption. Low Cd desorbability from goethite may be due to its specific adsorption and/or possibly as a result of Cd entrapment in the cracks or defects in goethite structure.     

土壤有机质对铊在土壤中吸附-解吸行为的影响

研究了土壤有机质对Tl＋在红壤和黄土2种土壤中的吸附-解吸行为的影响。结果表明,去除土壤有机质后红壤和黄土对Tl＋的吸附量均明显下降,下降幅度最高分别达到24.7%和28.2%,黄土的下降幅度大于红壤;黄土对Tl＋吸附率最高下降幅度约为20%,也高于红壤的15%。土壤有机质对Tl＋吸附的贡献率平均值分别是黄土39.2%、红壤32.8%。2种土壤对Tl＋的解吸量在去除有机质之后都明显增大,在初始Tl＋浓度较高的情况下,增大幅度明显;并且Tl＋的初始浓度越高,土壤在去有机质前后的解吸率相差就越大,在Tl＋最大处理浓度为20 mg/L时,红壤和黄土的解吸率增加分别达到60.8%和65.5%。     

Arsenic desorption from ferric and manganese binary oxide by competitive anions: significance of pH

Ferric and manganese binary oxide (FMBO) has been used to remediate an arsenic (As)-polluted river in China, but insufficient data was available to (1) evaluate its effects on the environment and (2) propose a feasible strategy of addressing the arsenic-bearing FMBO. The desorption behavior of arsenic in the presence of four competitive anions (i.e., phosphate, silicate, sulfate, and bicarbonate) at different concentrations was investigated with pH ranging from 3 to 11. The presence of these anions promoted the desorption of arsenic from arsenic-bearing FMBO and followed the sequence of phosphate > silicate > sulfate approximately equal to bicarbonate across a wide pH range. Desorption of arsenate (As[V]) was more significant than that of arsenite (As[III]). Sequence dissolution of arsenic-bearing FMBO particles by NH4-oxalate/oxalic acid and hydrochloric acid were performed. The laboratory results indicated that As(III) was primarily occluded in the crystalline parts of the FMBO. The desorption behavior of arsenic could be described by kinetic models using the Elovich and power function equations under different pH conditions and was related to the adsorption of phosphate and silicate. pH played an important role in the desorption of arsenic, because of its effects on the species distribution of anions, surface charge of the arsenic-bearing FMBO, and subsequent electrostatic forces between anions and FMBO.     

鼠李糖脂洗脱土壤中多氯联苯影响因素的研究

研究了由铜绿假单胞菌发酵产生的代表性生物表面活性剂鼠李糖脂（RL）对土壤中PCBs解吸的影响。结果表明,RL的种类与浓度、土壤污染类型、解吸时间、洗脱次数、pH以及离子强度对土壤中PCBs的洗脱有一定的影响,而温度对PCBs的洗脱影响很小。当RL浓度低于CMC时,对PCBs的洗脱没有明显的促进作用;当RL浓度高于CMC后,对PCBs的洗脱有显著的促进作用。具有较低HLB的单鼠李糖脂R2对PCBs的洗脱效果要优于二鼠李糖脂R1。人工污染土壤中PCBs的洗脱效果要高于陈化土壤。污染土壤中TOC的含量越高,PCBs的洗脱率越低。延长解吸时间和增加洗脱次数可增加土壤中PCBs的洗脱率。碱性环境（pH＞7）或增加RL溶液中的离子强度均有利于土壤中PCBs的洗脱。     

Effects of thermal desorption on the composition of two coking plant soils: impact on solvent extractable organic compounds and metal bioavailability

To evaluate the efficiency and the influence of thermal desorption on the soil organic compartment, contaminated soils from coking plant sites (NM and H) were compared to their counterparts treated with thermodesorption. The extractable organic matter, and the metal content and distribution with soil compartments were studied.In both thermodesorbed soils, PAH (polycyclic aromatic hydrocarbon) degradation exceeded 90%. However, the thermal desorption led not only to a volatilization of the organic compounds but also to the condensation of extractable organic matter.The treatments only affected the Fe and Zn distribution within the more stable fractions, whereas the organic compound degradation did not affect their mobility and availability.     

Effects of chemical oxidation on sorption and desorption of PAHs in typical Chinese soils

In situ chemical oxidation is a commonly applied soil and groundwater remediation technology, but can have significant effects on soil properties, which in turn might affect fate and transport of organic contaminants. In this study, it was found that oxidation treatment resulted mainly in breakdown of soil organic matter (SOM) components. Sorption of naphthalene and phenanthrene to the original soils and the KMnO₄-treated soils was linear, indicating that hydrophobic partitioning to SOM was the predominant mechanism for sorption. Desorption from the original and treated soils was highly resistant, and was well modeled with a biphasic desorption model. Desorption of residual naphthalene after treating naphthalene-contaminated soils with different doses of KMnO₄ also followed the biphasic desorption model very well. It appears that neither changes of soil properties caused by chemical oxidation nor direct chemical oxidation of contaminated soils had a noticeable effect on the nature of PAH-SOM interactions.     

Effects of SOM, surfactant and pH on the sorption-desorption and mobility of prometryne in soils

Sorption and desorption of the herbicide prometryne in two types of soil subjected to the changes of pH and soil organic matter and surfactant were investigated. The sorption and desorption isotherms were expressed by the Freundlich equation. Freundlich K_f and n values indicate that soil organic matter was the major factor affecting prometryne behavior in the test soils. We also quantified the prometryne sorption and desorption behavior in soils, which arose from the application of Triton X-100 (TX100), a nonionic surfactant and change in pH. Application of TX100 led to a general decrease in prometryne sorption to the soils and an increase in desorption from the soils when applied in dosages of the critical micella concentration (CMC) 0.5, 1 and 2. At the concentration below the CMC, the non-ionic surfactant showed a tendency to decrease prometryne sorption and desorption. It appeared that TX100 dosages above CMC were required to effectively mobilize prometryne. Results indicate that the maximum prometryne sorption and minimum prometryne desorption in soils were achieved when the solution pH was near its pK_a. Finally, the influence of TX100 on the mobility of prometryne in soils using soil thin-layer chromatography was examined.     

Adsorption, desorption, and mobility of permethrin in Malaysian soils

The adsorption, desorption, and mobility of permethrin in six tropical soils was determined under laboratory and greenhouse conditions. The six soils were selected from vegetable growing areas in Malaysia. Soil organic matter (OM) was positively correlated (r2 = 0.97) with the adsorption of permethrin. The two soils, namely, Teringkap 1 and Lating series with the highest OM (3.2 and 2.9%) released 32.5 and 30.8% of the adsorbed permethrin after four consecutive repetitions of the desorption process, respectively, compared to approximately 75.4% of the Gunung Berinchang soil with the lowest OM (1.0%) under the same conditions. The mobility of permethrin down the soil column was inversely correlated to the organic matter content of the soil. Permethrin residue penetrated only to the 10-15 cm zone in the Teringkap 1 soil with 3.2% OM but penetrated to a depth of more than 20 cm in the other soils. The Berinchang series soil with the lowest OM (1.0%) yielded leachate with 14.8% permethrin, the highest level in leachates from all the soils tested. Therefore, the possibility for permethrin to contaminate underground water may be greater in the presence of low organic matter content, which subsequently allows a higher percentage of permethrin to move downwards through the soil column.     

Role of organic acids in enhancing the desorption and uptake of weathered p,p'-DDE by Cucurbita pepo

Experiments were conducted to assess the effect of seven organic acids [succinic, tartaric, malic, malonic, oxalic, citric, ethylene-diaminetetraacetic (EDTA)] over a concentration range of two orders of magnitude (0.001-0.10 M) on the abiotic desorption of weathered p,p'-DDE and the extraction of polyvalent inorganic ions from soil. At 0.05 M all organic acids significantly increased contaminant desorption by 19-80%. Organic acids also increased the aqueous concentration of eight inorganic constituents extracted from soil, with at least a six-fold increase in the release of Al, Fe, Mn, and P at 0.001 M. Zucchini seedlings grown for 28 d in soil containing weathered p,p'-DDE (300 ng/g, dry weight) were periodically amended with distilled water, citric or oxalic acids (0.01 M). Plants receiving water removed 1.7% of the p,p'-DDE from the soil. Seedlings amended with citric or oxalic acids removed 2.1 and 1.9% of the contaminant, respectively, and contained up to 66% more contaminant in the shoot system than unamended vegetation. A second crop of untreated (distilled water) zucchini in the same soil removed more contaminant than the first crop (2.5%), although the addition of organic acids did not further enhance contaminant uptake. The data indicate that the addition of low molecular weight organic acids causes the partial dissolution of the soil structure through the chelation of inorganic structural ions, potentially enhancing bioavailability and having implications for the phytoremediation of persistent organic pollutants in soil.     

Effect of pH and the role of organic matter in the adsorption of isoproturon on soils

Equilibrium measurements were carried out with the herbicide isoproturon on natural adsorbents (brown forest-, chernozem-, sandy soils and quartz) in different buffered media (pH 5, 7, 8 phosphate buffer). Adsorption isotherms were fitted by a multi-step adsorption equation providing numerical information used in the environmental propagation models and risk assessment works. In the adsorption of the slightly polar isoproturon the dissolved organic matter of the soil and the pH play an important role. At molecular level, results are interpreted by taking into consideration the hydrophobic interaction and the formation of hydrogen bonds between the surface and the solute. The observed adsorption behavior indicates that the organic matter content of the soils and its soluble fulvic acid, alkaline soluble humic acid and insoluble humin fractions were considerable different. The chernozem soil containing the highest amount of insoluble organic fraction proved to be a very efficient adsorbent. The brown forest and the sandy soils exhibit rather similar adsorbent properties but at pH 7 the latter containing more fulvic acid adsorbs less isoproturon due to the enhanced solubility of the soil organic matter. In alkaline conditions the negatively charged solute and the surface repel each other and the hydrophobic interactions are also weaker than in neutral media.     

Desorption of copper and cadmium from soils enhanced by organic acids

The adsorption/desorption behavior of copper and cadmium on soils was investigated in this study. The adsorption isotherm of copper and cadmium conformed to Langmuir equation better than Freundlich equation. The effect of ionic strength, pH, and organic acid, including ethylenediamine tetraacetic disodium acid salt (EDTA), citric acid, oxalic acid and tartaric acid, on the desorption of copper and cadmium was studied. The desorption of copper and cadmium increased with the increase of ionic strength, while the desorption decreased with the rise of pH. The desorption of copper and cadmium enhanced by organic acids was influenced by pH. EDTA showed excellent enhancement on the desorption of both copper and cadmium; citric acid demonstrated great enhancement on the desorption of copper but negligible enhancement on the desorption of cadmium; oxalic acid enhanced the desorption of copper only at pH around 6.4 and enhanced the desorption of cadmium in the pH range from 6.4 to 10.7; tartaric acid slightly enhanced the desorption of copper but negligibly enhanced the desorption of cadmium. The desorption mechanism in the presence of organic acids were explained as the competition of complexation, adsorption and precipitation. The net effect determined the desorption efficiency. This study provided guidance for the selection of organic acids to enhance the electrokinetic (EK) remediation of copper and cadmium from contaminated soils.     

Sorption of weak organic acids in soils: clofencet, 2,4-D and salicylic acid.

The sorption behaviour of a new wheat hybridising agent (clofencet, 2-4-(chlorophenyl)-3-ethyl-2,5-dihydro-5-oxopyridazine-4-carboxylic acid) was investigated in batch equilibrium experiments and compared to that of two other organic acids (2,4-D and salicylic acid). Sorption coefficients Kd for the three compounds were determined in 18 Cambisols and Ferralsols. Kd values for clofencet were 0.3-9.4 l/kg for Cambisols and 2.1-68 l/kg for Ferralsols. Sorption of clofencet was strongly related statistically to that of salicylic acid. Sorption of clofencet and salicylic acid decreased exponentially with increasing solution pH in Cambisols whereas a bell-shaped curve was obtained for the sorption of salicylic acid in Ferralsols. Sorption of 2,4-D (2,4-dichlorophenoxyacetic acid) was not statistically related to the pH of the different soils. Positively charged oxide surfaces were shown to play a significant role in the sorption of clofencet and salicylic acid. The use of simple correlation and multiple linear regressions suggested that the main sorption mechanisms of clofencet in soils were likely to be ligand exchange on oxide surfaces and, to a lesser extent, cation bridging. Differences in the sorption behaviour of clofencet/salicylic acid and 2,4-D might be attributed to the possibility of the two former compounds forming bidentate complexes with metals.