Effect of organic matter on DOM sorption on lake sediments

The effect of organic matter on the sorption of dissolved organic matter (DOM) on lake sediments is critical to understanding the fate and transport of contaminants at the sediment–water interface in lake ecosystems. Results indicate that DOM sorption on sediment is largely due to ligand exchange between the DOM and hydroxyl groups, and the amount of DOC sorbed is a linear function of added DOC. With increasing organic matter content the sediment has lower binding strength, higher releasing ability for DOM, and the higher amount of DOM sorbed by sediment naturally. There was no clear difference before and after the sediment was treated with H₂O₂, but the constant b implied that after the sediments were treated DOC release was promoted. Organic matter in the sediment tends to impede the sorption of DOC and results in a remarkable decrease in DOC sorption rates.     

Rapid sampling of organic matter in flooded soils and sediments

Estuaries and Coasts - A coring system using a compressed air supply and a sediment shaking procedure using a soil dispersant are described which greatly simplify and shorten the task of...     

Arsenate sorption by reduced and reoxidised rice soils under the influence of organic matter amendments

Arsenic (As) sorptivity and acetate (pH 4.8) and oxalate (pH 3.0) extractable iron levels were monitored for 180 d, during and after flooding of two As contaminated soils. The effects of three different organic matter supplements/amendments, for example farm yard manure (FYM), municipal solid waste compost (MSWC) and sewage-sludge (SS) on the above parameter were also examined. In nonflooded soils, As sorptivity was mainly influenced by clay content. On flooding, there were large increases in acetate, oxalate extractable iron and As sorptivity. Organic matter addition increased the same parameters. Among the organic matters, SS showed greater effect on As sorption followed by MSWC and FYM. During flooding, As sorption is mainly dependent upon poorly crystalline iron oxide. During oxidation of previously flooded soils, levels of As sorptivity, acetate and oxalate extractable iron decreased rapidly, but did not return to the levels occurring before reduction. SS and MSWC served as binding agents for native and irrigation water As, thereby moderating the rapid As mobilization to the crop rizosphere.     

不同土壤有机质组分对憎水有机物的吸附机理研究

采用完全混合一步平衡反应实验方法，选择菲、萘、三氯苯和二甲苯作为憎水有机物(HOCs)的探针，研究了它们在土壤及其中的胡敏酸、胡敏素等有机质组分中的等温平衡吸附行为，探讨了非线性吸附的机制。结果表明，HOCs在水与土壤体系中表现为非线性吸附，其非线性的吸附行为主要受到土壤有机质(SOMs)的控制。SOMs具有高度不均匀的性质，HOCs表现出非线性吸附行为是其在不同的SOMs相扩散转移以及在相对聚结的胡敏素和“黑炭”的表面吸附的结果。     

Effects of low molecular weight organic acids on sorption and desorption behavior of p-chlorophenol by yellow earth

Low molecular weight organic acids （LMWOAs） are important components of root exudates. They play an important role in immobilizing and remobilizing contaminants in rhizospheric soil. Effects of four LMWOAs on the sorption and desorption behavior of p-chlorophenol by yellow earth was studied in batch mode. The results showed that the previous application of LMWOAs to enhanced adsorption capacity of p-chlorophenol of the soil in the order of maleic acid〉malic acid〉oxalic acid〉citric acid. However, when LMWOAs were applied to soil where p-chlorophenol had been previously adsorbed, substantial p-chlorophenol was desorbed from soil by oxalic acid, whereas citric acid, malic acid and maleic acid didn＇t desorb as much p-chlorophenol from soil as deionized water.     

Phosphorus desorption kinetics in two calcareous soils amended with P fertilizer and organic matter

We studied the effects of poultry manure and pistachio compost with and without phosphorus fertilizer on the kinetics of phosphorus desorption in two calcareous soils of Kerman and Koohbanan farms in the southeastern of Iran. For this purpose mono potassium phosphate, at rates of 0, and 100 parts per million of phosphorus, and air-dried manure, at rates of 0 and 4% were mixed with the soils. The soils were incubated at 24–25°C and near field capacity for 90 days in the greenhouse. Afterwards, the desorption of P was studied by the successive extraction with 0.5 M NaHCO₃. The results of this research indicated that application of OM and fertilizer P combined increased P recovery in each of the extraction time, adding poultry manure and 100 mg phosphorus together to the soils, increased P desorption more than pistachio compost in the soils. The phosphorus desorption rate was initially rapid and then became slower until equilibrium was approached. Kinetic data were best described by power function and simple Elovich equations. Subsequent to these equations, parabolic diffusion equation was also well fitted the time-dependent P desorption data.     

Toluene sorption behavior on soil organic matter and its composition using three typical soils in China

The effect of soil organic matter (SOM) content and composition on sorption behavior of toluene for fluvo-aquic, red and black soils in China was investigated in batch experiments. Tested SOM was fractionated into two primary sorptive domains (‘soft’ and ‘hard’) to explain the dependence of sorption behavior on SOM composition. All the tested soils exhibited similar sorption kinetics and nonlinear sorption isotherms. Soils with high SOM content possessed a high sorptive capacity. Clay minerals also contributed to the sorptive capacity, especially for fluvo-aquic and red soils with low SOM content. In comparison, after removing most ‘soft’ SOM fraction from soils through hydrogen peroxide treatment, the residual ‘hard’ SOM fraction of three soil samples exhibited a slower sorption rate and a less sorption capacity compared to the untreated soil samples. The nonlinear degree of sorption was positively correlated with the content of ‘hard’ SOM for all soil samples. This is explained by the combined effect of SOM content and the composition on toluene sorption rates, sorption capacity and nonlinear degree of sorption of three typical soils in China.     

Models of natural organic matter and interactions with organic contaminants

Adsorption of organic contaminants onto soils, sediments and other particulates has the potential to be a major controlling factor in their bioavailability, fate and behavior in the environment. Models for estimating the amount and stability of sorbed organic contaminants based on the fraction of organic carbon in a soil or sediment can oversimplify the process of sorption in the environment. In order to help understand sorption of organic contaminants in soils and sediments, we modeled various components of natural organic matter (NOM) that are possible substrates for sorption. These substrates include soot particles, lignin, humic and fulvic acids. The molecular scale interactions of selected aromatic hydrocarbons with different substrates were also simulated. Results of the simulations include the 3-D structures of the NOM components, changes in structure with protonation state and solvation and the sorption energy between PAH and substrate. This last parameter is an indicator of the amount of contaminant that will sorb and the energy required to free the contaminant from the substrate. Although the simulation results presented in this paper represent a first-order examination of NOM and contaminant interactions, the findings highlight a number of essential features that should be included in future molecular models of NOM and contaminant sorption.     

Experimental modeling of platinum sorption on organic matter

In connection with the discovery of a new type of Pt deposit in low-rank brown coals and black shales, the interaction of Pt-bearing aqueous solutions with fractionated organic matter (asphaltenes and asphaltenic acids) was studied at 200–400°C and 1 kbar total pressure. It was found that chemical sorption onto the organic matter lowers Pt content in the aqueous solutions by about two orders of magnitude relative to organic-free systems. Thermal maturation of the asphaltenes leads to its aromatization and concomitant sorption of Pt from n×10⁻⁴ mPt (mol per kg of dry matter) at 200°C to n×10⁻² mPt at 400°C. Thus, the Pt chemisorption on activated carbonized organic matter may be an effective mechanism of Pt accumulation in C-bearing rocks.     

Effects of cations and anions on iron and manganese sorption and desorption capacity in calcareous soils from Iran

This study investigated the effect of cations and anions on the sorption and desorption of iron (Fe) and manganese (Mn) in six surface calcareous soil samples from Western Iran. Six 10 mM electrolyte background solutions were used in the study, i.e., KCl, KNO₃, KH₂PO₄, Ca(NO₃)₂, NaNO₃, and NH₄NO₃. NH₄NO₃ and NaNO₃ increased the soil retention of Fe and Mn, whereas Ca(NO₃)₂ decreased the soil retention of Fe and Mn. Iron and Mn sorption was decreased by NO₃ ^? compared with H₂PO₄ ^? or Cl^?. The Freundlich equation adequately described Fe and Mn adsorption, with all background electrolytes. The Freundlich distribution coefficient (K _F) decreased in the order H₂PO₄ ^? > Cl^? > NO₃ ^? for Mn and H₂PO₄ ^? > NO₃ ^? > Cl^? for Fe. The highest sorption reversibility was for Fe and Mn in competition with a Ca²⁺ background, indicating the high mobility of these two cations. A MINTEQ speciation solubility model showed that Fe and Mn speciation was considerably affected by the electrolyte background used. Saturation indices indicated that all ion background solutions were saturated with respect to siderite and vivianite at low and high Fe concentrations. All ion background solutions were saturated with respect to MnCO_3(am), MnHPO₄, and rhodochrosite at low and high Mn concentrations. The hysteresis indices (HI) obtained for the different ion backgrounds were regressed on soil properties indicating that silt, clay, sand, and electrical conductivity (EC) were the most important soil properties influencing Fe adsorption, while cation exchange capacity (CEC), organic matter (OM), and Mn-DTPA affected Mn adsorption in these soils.     

Europium sorption to sediments in the presence of natural organic matter: A laboratory and modeling study

Cellulosic materials, such as wood, paper products and cardboard that have been co-disposed with low-level nuclear waste have been shown to produce leachate with natural organic matter (NOM) concentrations of hundreds of mg/L C and, as such, have the potential to influence the fate and transport of radionuclides in the subsurface environment. The objective of this study was to examine the influence of NOM on the sorption of Eu (an analogue for trivalent radionuclides) to two coastal plain sediments from the US Department of Energy’s Savannah River Site. Particular attention was directed at quantifying Eu interactions with NOM sorbed to sediments (NOM_sed) in laboratory experiments and developing conditional stability constants for that interaction using the thermodynamic equilibrium speciation model MINTEQA2. Europium sorption to the two sediments systematically increased as pH increased from 3.9 to 6.7. With increasing additions of NOM to the aqueous phase from 0 to 222 mg/L C, Eu sorption initially increased to a maximum at 10 mg/L C NOM_aq and then decreased with increasing NOM_aq concentrations. Increases in Eu sorption at low NOM additions was attributed to the sorption of NOM to the sediment surface increasing the number of sorption sites on the low cation-exchange capacity sediments and/or increasing the association constant (log K) for the Eu-sediment surface reaction. Decreases in Eu sorption at higher NOM levels was attributed to Eu_aq complexation to NOM_aq being more favored than Eu sorption to the solid phase. A component additivity model was developed to describe the Eu–NOM-sediment system by the additive effects of the three binary system models: Eu–NOM, Eu-sediment and NOM-sediment. The model generally captured the data trends in the ternary system. Conditional stability constants developed from the experimental data for the complexation of Eu to NOM_sed were as much as four orders of magnitude greater than Eu complexation with NOM_aq, presumably due to the NOM_sed deriving additional negative (attractive) charge from the sediment surface. At high initial NOM_aq levels, >99 mg/L C, the model captured the trend of reduced Eu sorption but tended to over-estimate Eu sorption. The additivity approach of combining binary models to form a ternary model was only successful when the unique complexation properties of the NOM_sed were properly calculated.     

Metal sorption onto soils loaded with urban particulate matter

The potential effect of urban particulate matter (PM) accumulation on metal sorption onto two contrasting soils (Chernozem and Fluvisol) was investigated in a batch sorption experiment. While the Freundlich isotherms did not indicate any effect of PM addition to the soils, the Langmuir isotherm allowed us to estimate the potential behaviour of the PM in the soil. The PM added to the Chernozem did not lead to substantial changes in sorption of Cd, Cu, Mn, Ni, Pb, and Zn. On the contrary, the presence of PM in the Fluvisol increased the number of potential sorption sites in the soil. However, the results of the approximation showed a lower affinity of Cd, Mn and Ni for the Fluvisol and a better stability and a lower bioavailability of these elements in the Chernozem. In the case of Pb and Cu, no significant changes were observed in PM-enriched soils regardless of the soil properties.     

Organic matter in small mesopores in sediments and soils

The three-way correlation among organic matter concentrations, specific surface area and small mesopores observed for many soils and sediments led to the hypothesis that enclosure within the pores might explain the apparent protection of organic matter by minerals. We test this hypothesis by examining whether the bulk of organic matter resides within small mesopores. Pore volumes as a function of pore width were measured before and after organic matter removal, and the volume differences ascribed to organic matter filling of pores. Minor changes in small mesopore size distributions upon treatments such as centrifugation and muffling indicate the robustness of the mineral matrices that form these pores. We developed an additional method to assess organic matter densities using high-resolution pycnometry, and used these densities to convert pore volumes to organic matter contents. Although smaller mesopores are shown to have sufficient volumes to contain significant fractions of the total organic matter, only small fractions of total organic matter were found to reside in them. These results are consistent with preferential association between organic matter and aluminous clay particle edges, rather than the largely siliceous clay faces that contribute most surface area and form pore walls. While simple enclosure within smaller mesopores cannot, therefore, explain protection, network effects working at larger size scales may account for exclusion of digestive agents and hence organic matter protection.     

Kinetics of copper desorption from soils as affected by different organic ligands

Desorption of Cu and low molecular weight dissolved organics are the primary factors that impact fate and transport of Cu in soils. To improve predictions of the toxicity and threat from Cu contaminated soil, it is critical that time-dependent desorption behavior be understood. In this paper, the effect of organic ligands citrate, malate, and succinate on the kinetics of Cu desorption from contaminated soils varying widely in soil characteristics was investigated at 25° C and the soils used were referred to as clay, calcareous and sandy soils. The amount of Cu released by the used organic ligands varied greatly with physicochemical properties of the soils. The rate of Cu release by different extractants was in the order citric > malic > succinic, which was consistent with the stability constants of Cu complexes with these ligands. The modified Freundlich and the Elovich and Parabolic diffusion models were used to describe dsorption of Cu²⁺ from the three studied soils as affected by the organic ligands. All of the models fit the data well with correlation coefficients ranging from 0.83 to 1.00 (P < 0.01). Each Model has a set of assumptions for the different physical and chemical properties of the systems to which they are being applied. The uses of these equations yield different magnitudes for the calculated variable, but the relationships between the soil + organic ligands and their effect (i.e., increase or decrease) on these variables are the same. Such information is critical, since Cu is used in a variety of industrial and manufacturing processes and is one of the most common contaminants found at hazardous waste sites.     

Effects of geosorbent and solution properties on sorption and desorption of PAHs

Characteristics of phenanthrene and pyrene’s sorption and desorption on two local soils in solutions of simulated groundwater, simulated lung fluid, and simulated saliva were studied with batch equilibrium experiments to understand the fate of PAHs in the karst region of southwestern China and to assess the environmental exposure and the health risk of PAHs. The results showed that the sorption and desorption isotherms of phenanthrene and pyrene on two target soils in the three solution systems could be adequately described by the Freundlich model, while the fitted isotherm parameters for the simulated groundwater solution distinguished notably from those for the simulated body fluid solutions. For the sorption experiments, in the simulated groundwater, the n values were 0.722 and 0.672 for phenanthrene and were 0.724 and 0.663 for pyrene, respectively, on the yellow soil and the limestone soil; The log K_F values were 3.118 and 3.323 for phenanthrene and were 3.648 and 3.846 for pyrene, respectively, on the yellow soil and the limestone soil. In the simulated body fluids, the n values for phenanthrene and pyrene ranged from 0.622 to 0.836 and from 0.590 to 0.865, respectively, and the log K_F values of phenanthrene and pyrene ranged from 2.845 to 3.327 and from 3.344 to 3.779, respectively. For the desorption experiments, in the simulated groundwater, the n values were 0.662 and 0.744 for phenanthrene and were 0.702 and 0.647 for pyrene, respectively, on the yellow soil and the limestone soil. The log K_F values were 3.666 and 3.686 for phenanthrene and were 4.128 and 4.225 for pyrene, respectively, on the yellow soil and the limestone soil. In the simulated body fluids, the n values for phenanthrene and pyrene ranged from 0.612 to 0.668 and from 0.631 to 0.819, respectively, and the log K_F values of phenanthrene and pyrene ranged from 3.134 to 3.407 and from 3.533 to 3.839, respectively. The limestone soil had relatively higher log K_F values but lower K_OC values compared to those of the yellow soil, indicated that the nature of sorbent soils played the dominant role in sorption and desorption behaviors of PAHs. The experimental results showed a remarkable differences in sorption and desorption behaviors of PAHs in simulated body fluids and groundwater. The nonlinearities of measured isotherms and the measured sorption capacities of soils in simulated body fluids were significantly lower than corresponding those in the simulated groundwater, and HI values for simulated body fluids systems were significantly smaller than corresponding those for the simulated groundwater systems. The results underscore cautions in assessing environmental exposure and health risks of PAHs based on their sorption–desorption data in simulated groundwater as this is traditionally done.

     

Competitive sorption and desorption of cadmium and lead in paddy soils of eastern China

To assess the competitive sorption and desorption of cadmium (Cd) and lead (Pb), batch equilibrium experiments were performed using single- and binary-metal solutions in surface samples of three paddy soils from eastern China. Sorption isotherms were well fitted with one-metal and competitive Langmuir equation for single- and binary-metal system, respectively. The distribution coefficient (K _d) values were K _{d single} (Pb) > K _{d binary} (Pb) > K _{d single} (Cd) > K _{d binary} (Cd), indicating that Pb was stronger sorbed by these soils than Cd in binary metal system. Soils with high pH and clay content had the greatest sorption capacity as estimated by the maximum sorption parameter (Q). The co-existence of both metals reduces their tendency of sorption, whereas Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (b) in binary sorption system was greater than that in single sorption system for all soils (b < b ₁), indicating that competition for sorption sites promote the retention of both metals into more specific sorption sites. Sorption of Cd and Pb decreased soil pH by 1.61 U for YRS, 1.39 U for PCS, and 0.91 U for SLS. The decreases of pH in binary metal system were greater than in single-metal system for three soils. Cadmium and Pb desorption increased with increasing Cd and Pb sorption saturation for all soils; however, Cd desorption ratio in binary metal system (d _Cd*) was much greater than Pb (d _Pb*), indicating that under the competitive sorption conditions, the sorbed Cd was more readily desorbed from the soils than the sorbed Pb.     

Sorptive stabilization of organic matter in soils by hydrous iron oxides

Strong correlations between iron oxides (FeOx) and organic matter (OM) in soils have implied the importance of the former in stabilizing the latter. One mechanism thought to be important in this stabilization is sorption. We tested this possibility by reductively dissolving FeOx in a wide variety of soils and measuring the organic carbon (OC) that was solubilized. The OC dissolved from non-FeOx phases via anion exchange was corrected for by parallel control extractions. The resultant pool, reductively soluble OC, made up a minor amount of total soil OC in all but one of these soils, indicating that simple sorption reactions do not stabilize the bulk of soil OC in most mineral soils. OC:Fe ratios in the extracts from 2/3 of these soils were less than 0.22 (wt/wt), consistent with a sorbed state for this OC and showing that OC sorption by FeOx in these soils is limited by the amount of FeOx. The remaining soils had low pH and high OM concentrations; their higher OC:Fe ratios indicate inclusion of precipitated organo-Fe complexes in the extracts, which are likely only partially extracted by our method. The high volumetric ratios of OM to FeOx found in correlations between them from the literature are inconsistent with a dominant sorption control and point instead to stabilization to other mechanisms such as organo-Fe complexes or ternary associations among FeOx, OM and other minerals.