Effects of dissolved organic matter from sewage sludge on the atrazine sorption by soils

The effects of dissolved organic matter (DOM), water soluble organic matter derived from sewage sludge, on the sorption of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-trazine) by soils were studied using a batch equilibrium technique. Six paddy soils, chosen so as to have different organic carbon contents, were experimented in this investigation. Atrazine sorption isotherms on soils were described by the linear equation, and the distribution coefficients without DOM (K_d) or with DOM (K_d ^*) were obtained. Generally, the values of K_d ^*/K_d initially increased and decreased thereafter with increasing DOM concentrations of 0–60 mg DOC · L^?1 in soil-solution system form. Critical concentrations of DOM (DOM_np) were obtained where the value of K_d ^* was equal to K_d. The presence of DOM with concentrations lower than DOM_np promoted atrazine sorption on soils (K_d ^* > K_d), whereas the presence of DOM with concentrations higher than DOM_np tended to inhibit atrazine sorption (K_d ^* < K_d). Interestingly, DOM_np for tested soils was negatively correlated to the soil organic carbon content, and the maximum of K_d ^*/K_d (i.e.K _max) correlated positively with the maximum of DOM sorption on soil (X_max). Further investigations showed that the presence of hydrophobic fraction of DOM evidently promoted the atrazine sorption on soils, whereas the presence of hydrophilic DOM fraction obviously tended to inhibit the atrazine sorption. Interactions of soil surfaces with DOM and its fractions were suggested to be the major processes determining atrazine sorption on soils. The results of this work provide a reference to the agricultural use of organic amendment such as sewage sludge for improving the availability of atrazine in soils.     

Pesticide desorption from soils facilitated by dissolved organic matter coming from composts: experimental data and modelling approach

Dissolved organic matter (DOM) interaction with pesticides was examined studying the ability of DOM to desorb 8 pesticides previously sorbed to soil. DOM was originating from municipal waste composts at two maturity degrees, recovered at 20°C and by hot-pressurised subcritical water. Pesticide desorption depended on their previous sorption on soil. When sorption was low (K_OC ≤ 50, sulcotrione, metalaxyl), water was more efficient than DOM for desorption. On the contrary, when sorption was high (K_OC ≥ 2000, trifluraline), little effect of DOM was observed. For the moderately sorbed pesticides, DOM favoured pesticide desorption compared to water. For the lowest sorbed pesticides (K_OC ≤ 100), hysteresis was increased with larger proportions of DOM extracted with subcritical-water. Dissolved organic matter extracted from fresh-immature compost had larger capacity to mobilize the sorbed pesticides than the DOM from the mature compost. The pesticide desorption resulted from the positive and competitive interactions between pesticide, DOM and soil surfaces. These interactions were modelled considering separate partitioning coefficients. A general equation allowed the deduction of specific coefficients describing interactions in solution between pesticides and the non-sorbed fraction of DOM remaining in solution. This fraction was supposed to contain the most hydrophilic fraction of DOM and was able to interact with the most polar pesticide (amitrol). When pesticide hydrophobicity increased, the partitioning between pesticide and DOM decreased. Modelling the three-phase system (liquid, DOM and solid phases) pointed out that the solid phase played the most important role on pesticide behaviour through the sorption process of DOM and pesticides.     

Influence of the Interactions Between Black Carbon and Soil Constituents on the Sorption of Pyrene

Biochar (a kind of black carbon (BC)) has been advocated as a promising additive to farmland, thus it is crucial to understand the influence of BC on the fate of hydrophobic organic chemicals (HOCs) when they exist in soil. This study explored the sorption of pyrene onto a BC sample obtained by pyrolyzing pine sawdust, two soils, clay (kaolinite), and the mixtures thereof to investigate the influence of the interactions between BC and soil constituents on the sorption of HOCs and the mechanisms therein. Sorption of pyrene onto soil?BC mixtures was significantly less than that predicted by the sum of the individual soil and BC sorption, indicating that the sorption of pyrene onto soil and BC did not occur independently. The reduction of BC sorption capacity in soil seemed primarily to be caused by soil dissolved organic matter (DOM), which attenuated pyrene sorption onto BC by 18.7%?40.3% (within pyrene equilibrium concentration range of 0.05?0.5 S _w). These were likely due to the blockage of micropores, reduced accessibility of sorption sites, and binding of pyrene by DOM in aqueous solution. In addition to the DOM effect, kaolinite also diminished pyrene sorption onto BC to some extent, which suggested additional interaction between BC and soil particles. Pyrene sorption onto the soil?BC mixtures varied with water content and contact time. The influence of wet versus dry conditions and contact time on the K_oc of pyrene was more obvious when pyrene equilibrium concentrations were lower. The effect of aging also varied with soil properties. In summary, BC could not behave independently in soil, and its sorption capacity was changed by its interactions with soil constituents, which may be influenced by soil properties, environmental condition, and contact time.     

表面活性剂对链霉素在内蒙古牧区土壤中吸附解吸的影响

通过静态吸附实验,研究了3种不同类型的表面活性剂(阳离子:十六烷基三甲基溴化铵,CTAB;阴离子:十二烷基苯磺酸钠,SDBS;非离子,曲拉通100,TX-100)对链霉素(Streptomycin,STR)在内蒙古牧区土壤中吸附解吸的影响。结果表明,3种表面活性剂的存在均会增加STR在土壤中吸附的线性程度。CTAB的存在抑制了STR在土壤表面的吸附同时抑制了STR的解吸,然而SDBS的存在降低了STR在土壤中的吸附量并增加了吸附过程的可逆性。与CTAB和SDBS不同,TX-100对STR在土壤中的吸附的影响取决于其添加浓度。低浓度的TX-100对STR的吸附促进作用大于高浓度。随着TX-100浓度的增加,TX-100对STR的增溶作用加剧。促使吸附在土壤表面的STR迁移到水相中,从而抑制了STR的吸附,进而促进了STR的解吸。     

Fate and Transport of High Explosives in a Sandy Soil: Adsorption and Desorption

Several areas of the Massachusetts Military Reservation (MMR) have soils with significant levels of high explosives (HE) contamination because of a long history of training and range activities (such as open burning, open detonation, disposal, and artillery and mortar firing). Site-specific transport and attenuation mechanisms were assessed in sandy soils for three contaminants of concern: the nitramine hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and the nitroaromatics 2,4-dinitrotolune (2,4-DNT) and 2,4,6-trinitrotoluene (TNT). For all three contaminants, linear distribution coefficients (K_d) were dependent on the fraction of organic carbon in soil. The nitroaromatics sorbed much more strongly than RDX in both soils. Over 120 hours, the desorption rate of RDX from field contaminated surface soil was much slower than its sorption rate, with the desorption K_d (1.5 L/kg) much higher than K_d for sorption (0.37 L/kg). Desorption of 2,4-DNT was negligible over 120 hours. Thus, applying sorption-derived K_d values for transport modeling may significantly overestimate the flux of explosives from MMR soils. Based on multiple component column transport tests, RDX will be the most mobile of these contaminants in MMR soils. In saturated columns packed with uncontaminated soil, RDX broke through rapidly, whereas the nitroaromatics were significantly attenuated by irreversible sorption or abiotic transformations.     

Impact of Clay Minerals and DOM on the Competitive Sorption/Desorption of PAHs

Two model compounds were used to investigate sorptive phenomena of a silty-sand soil under single and binary solute systems at different concentrations. In the sorption isotherms, the presence of phenan-threne (PHE) exhibited a statistically significant (P<0.05) sorption competition over pyrene (PYR), regardless of the concentration. PYR influenced the PHE isotherms only when it was present at 15?mg/L. The concentration dependence in sorption competition was only evident for the more hy-drophobic PYR. In the presence of PHE, the fraction of desorbed PYR was significantly increased with an increase in PYR concentration. PHE desorption enhancement was the most observable with the higher initial concentration (15?mg/L). However, the presence of PYR did not affect PHE desorption. This study found that, based on equivalent solid mass, soils containing only clay minerals sorbed 12.2% more PHE than soils with only soil organic matter (SOM) for 3?mg/L PHE. Clay minerals also impacted desorption as evidenced by a 65% decrease in desorbed PYR fraction compared with when the soil only contained SOM. The dissolved organic matter (DOM) amendment did not increase desorption. Instead, PHE desorption was significantly inhibited by the added DOM. For this study, co-sorption was found to be the mechanism for the inhibited desorption.     

Characteristics of Copper Sorption by Various Agricultural Soils in China and the Effect of Exogenic Dissolved Organic Matter on the Sorption

To explore the effect of exogenic dissolved organic matter (DOM) on Cu(II) sorption in agricultural soils, 26 agricultural soils were collected across China. Exogenic dissolved organic matter, extracting from wheat straw (DOM_W) and swine manure (DOM_S), respectively, were added to the soils to conduct a series of batch sorption and characterization experiments. The solid-liquid partition coefficient (K_d) ranged from 0.02 to 76.46 L g^?1, suggesting different Cu(II) sorption on various soils. PCA analysis indicated that pH, free Fe/Al oxides, carbon, and total Cu content had a significant positive relationship with the Cu(II) sorption, respectively. And the contribution rate of pH was the highest (38.15%). Moreover, DOM markedly inhibited the Cu(II) sorption in alkaline soils while promoted the Cu(II) sorption in acidic soils, which were interacted by the soil properties and DOM characteristics. The effect of DOM_S on Cu(II) sorption were more obvious than DOM_W, which were further confirmed by Fourier transform infrared (FTIR) spectroscopy. FTIR also showed Cu(II) was primarily adsorbed on the specific functional groups, such as CO, OH, and CO, providing direct evidences for the binding of Cu(II) with DOM. This study can guide the rational use of organic fertilizers, and also provide baseline knowledge for the prevention and control of soil pollution.     

Fate of Nitroglycerin and Dinitrotoluene in Soil at Small Arms Training Ranges

Nitroglycerine (NG), 2-4-dinitrotoluene, and 2,6-dinitrotolune (DNTs), commonly deposited on soil during military training, have been identified as potential threats to groundwater at Camp Edwards on the Massachusetts Military Reservation. Accordingly, a series of experiments were performed to obtain site-specific sorption coefficients (K_d) for use in computer simulations. Experiments employing aqueous, reagent-grade contaminants, with a biocide added, showed NG underwent limited sorption onto the sandy soil from the study area. DNTs were retained to a greater extent. Desorption experiments demonstrated a portion of the contaminants were irreversibly bound. Soil characteristics had a significant effect on K_d, apparently because of changes in organic carbon, cation exchange capacity, and/or clay content with depth in the soil profile. Experiments with NG containing soil, fresh, unfired propellant, or with freshly fired propellant produced partitioning values considerably higher than those observed with reagent grade material added from solution—demonstrating dissolution as the rate-limiting step. The apparent K_d also increased significantly when no biocide was used, thereby indicating a major role for biodegradation. In addition, NG and the DNTs introduced during military training did not leach from site soil at the small arms ranges studied. Taken together these data demonstrate that K_ds from laboratory experiments using dissolved reagent-grade compounds are not appropriate for predicting NG and DNT mobility in the field.     

The biological and physico-chemical uptake of radiocesium by particulate matter of natural origin (Baltic Sea)

The kinetics of radiocesium (¹³⁷Cs) uptake by natural suspended matter collected from coastal waters in the southern Baltic has been studied under laboratory conditions. The uptake of radiocesium from seawater by the suspended matter took place immediately after introduction of the isotope and attained equilibrium within a few hours. Summer and winter suspended matter displayed equal K_d values, indicating similar sorption characteristics of radiocesium. The amounts of radiocesium sorbed from sea water were proportional to the suspended matter concentration studied,i.e. up to 312 mg dry wt dm^–3. The relative uptake of radiocesium by live and dead plankton appeared to be the same. The desorption of radiocesium from dead plankton proceeded more rapidly and more intensively than sorption. There are no significant differences between the K_d values for plankton determined in laboratory experiments and those found for plankton populations under field conditions.     

Medium-induced inhibition of microbial adsorption to nickel and activated charcoal

Equilibrium adsorption studies on Escherichia coli and Saccharomyces sp. revealed the capacity and affinity of these organisms for the surfaces of powdered charcoal and nickel. In simple salt solutions both organisms readily adsorbed to each solid with an affinity and maximum loading capacity individual to each cell-solid combination. In the presence of common growth media (lab-lemco, nutrient broth, peptone, and yeast extract, individually at a concentration of 1.3%), each medium substantially inhibited adsorption. Each medium contained a protein-aceous constituent as determined by ultraviolet (UV) analysis. The degree of inhibition was relative to medium concentration present during assay. Cell wall extracts from whole-yeast cells also effectively inhibited adsorption. Cells adsorbed in the presence of sodium chloride solutions were susceptible to subsequent desorption by nutrient broth.     

Depletion of Selenium in Soil Solution due to its Enhanced Sorption in the Rhizosphere of Soybean

The effect of plant roots on selenium (Se) mobility in soil was studied by a large-scale pot experiment in order to understand the environmental behavior of Se in agricultural soils under plant growth conditions. Soybean plants (Glycine max (L.) Merrill) were grown in a greenhouse for 84 d. The concentrations of Se and major elements (K, Ca, Mg, Na, and Al) in the soil solutions and in the plants were measured at different growth periods. Concentrations of Se and major cations in soil solution decreased as the soybean plants grew, while the concentrations of Al increased. It was assumed that the soybean roots released H⁺ with the uptake of cations; consequently, due to the acidification of the rhizosphere, Al³⁺ was released starting from the soil solid phase. The decreased Se concentration in the soil solution should be due to the enhancement of Se sorption onto the soil solid phase. The increase of Se sorption level in the rhizosphere was examined in a small-scale pot experiment. The soil–soil solution distribution coefficient of Se (K _d-Se) was observed as an index of Se sorption level. K _d-Se clearly increased in the rhizosphere soil after cultivation. The effects of pH and Al³⁺ in the rhizosphere on Se sorption were assessed by K _d-Se measurements at different levels of HCl and AlCl₃. In this third experiment, a decrease in pH increased K _d-Se values, but no specific effect was observed on Se sorption due to increased Al³⁺. These results show that the Se mobility in agricultural soil could be decreased by plant roots under plant growth conditions due to enhanced Se sorption in the rhizosphere.     

Sorption of caesium,iodine and sulphur in solution to the adaxial leaf surface of broad bean (Vicia faba L.)

The interception by crop canopies of radionuclides in rainfall can be important in determining radiation exposures to animals and man. Data were obtained on the sorption and desorption of radionuclides on the adaxial surfaces of fully expanded bean leaves by exposing them to ionic forms of caesium (Cs⁺), iodine (I⁻) or sulphur (SO₄²⁻) over a six order of magnitude concentration range. The accumulation of each element was determined as a time course over a 48 h period using radioactive labels (¹³⁷Cs, ¹²⁵I or ³⁵S, respectively). Time- and concentration-dependent sorption of each element to the leaf surface was analysed to determine: (a) the leaf surface-solution distribution coefficient (K_d) at equilibrium and (b) the sorption and desorption rate coefficients for each element over the range of concentrations investigated. It was expected that Cs⁺ would show a stronger tendency to sorb to the leaf surface than both I⁻ and SO₄²⁻ because of the cation exchange properties of the cuticular membrane. The K_d for Cs⁺ was approximately 90× greater than that for SO₄²⁻ but 5× less than that for I⁻. This is thought to be due to either (a) the highly organophilic nature of iodide and the relatively high iodine number of cuticular waxes on plant leaf surfaces or (b) the possible oxidation of I⁻ to I⁰ or IO₃⁻, with consequently enhanced leaf surface sorption. Based on data obtained in this study, ranges and best estimates of sorption and desorption rate coefficients are presented for Cs⁺, I⁻ and SO₄²⁻ for use in modelling the interception of radioactive Cs, I and S in rainfall by crops.     

Comparative Sorption of Phenanthrene and Benzo[α]pyrene to Soil Humic Acids

Sorption of phenanthrene (Phen) and benzo[α]pyrene (BaP) by humic acids (HAs) extracted from four typical soils in China, including cinnamon soil, fluvo-aquic soil, red soil, and mountain meadow soil were investigated. All sorption data were fitted well by the Freundlich model, but BaP exhibited stronger and more nonlinear sorption than Phen by a given HA. For Phen isotherms, there was a positive relation between K _oc values and aliphaticity of HAs, whereas a negative correlation was observed between n values and aliphaticity. This indicated the importance of aliphatic groups in Phen sorption capacity and nonlinearity. Compared to Phen, a similar trend was obtained between n values of BaP and aliphaticity or aromatic carbon. However, no correlation existed between K _oc values for BaP and aliphaticity or aromatic carbon.     

Impact of Dissolved Organic Matter on the Desorption and Mineralization Rates of Naphthalene

The persistence of organic contaminants in plant-soil systems will be largely determined by the basic processes controlling bioavailability: desorption and biodegradation. Both processes can be affected by the presence of and variations in dissolved organic matter (DOM). To evaluate potential effects of DOM in surface soil remediation systems, the kinetics of naphthalene desorption from soil and mineralization in soil solution in the presence of DOM were studied in completely mixed batch reactors (CMBRs). Three different DOM solutions were studied. These were obtained from water extraction of two different soils (muck-highly organic and alfalfa field-agricultural) and a third prepared by reconstituting a fulvic acid reference standard purchased commercially. Neither the desorption rate nor equilibrium partitioning of naphthalene was affected by the presence of varying DOM solutions. The effect on mineralization was evaluated based on an evaluation of a first-order rate constant produced by nonlinear regression of data fitted to a ¹⁴CO₂ production model. For the muck DOM solution, alfalfa DOM solution, and fulvic acid DOM solution, first-order rate constants were 0.0474, 0.0657, 0.0422 min_?1, respectively. Using uncertainty analysis, these differences were found not to be significant at a 90% confidence level. Although not apparent in this data, the impact of DOM on the mechanisms of desorption and biodegradation in a plant -soil environment may be important for other contaminant/organism/soil combinations. With the increased interest in phytoremediation and land farming as means of treating organic contaminants, further investigation of such interactions may be warranted.     

Naproxen Adsorption-Desorption in a Sandy Aquifer Matrix: Characterisation of Hysteretic Behavior at Two Different Temperature Values

Adsorption/desorption processes (sorption isotherms) of Naproxen in a sandy aquifer matrix sediment were investigated using batch tests to compare Naproxen sorption behavior at 15°C and 25°C. Both temperatures are representative of the aquifer media and environmental conditions. Adsorption was well described by linear isotherms with low sorption affinity to aquifer material (K_d of 0.4 μg kg^?1) at both temperatures (15°C and 25°C). Desorption isotherm coefficients at 15°C and 25°C were 5.0 and 4.9, respectively. Naproxen hysteresis indices were between 9.98 and 10.8, indicating that a Naproxen fraction may be irreversibly fixed in the aquifer media, being higher at 25°C (10.88) compared to 15°C, showing a decreasing trend with increasing compound concentration at 15°C. The low sorption of Naproxen leads to potential leaching to groundwater if present in irrigation water, and its prevalence in an aquifer media when directly injected in wells for groundwater recharge.     

Sorption of Methylene Blue by an Oscillatoria sp.–Dominated Cyanobacterial Mat

The ability of an Oscillatoria sp.–dominated cyanobacterial mat in sorbing methylene blue (MB), a cationic dye, was investigated using the batch contact method. The sorption of MB onto the powdered biomass was not significantly influenced by initial pH (2–10) and temperature (5–45°C) of the solution. MB sorption occurred slowly, requiring 1–8 h for the establishment of equilibrium. A slow attainment of equilibrium seems to be related with the large size of MB ions. The isotherm data of MB sorption by the mat biomass could effectively fit to Langmuir and Freundlich models. The maximum MB sorption capacity (q _max) of the test biomass was 78.43 mg g^?1, which changed little with variation in biomass concentration. Moreover, the test biomass could efficiently sorb MB from solution in presence of Na⁺, K⁺, and Ca²⁺, which usually occur at high concentrations in natural waters, and also in presence of Cd²⁺. These particular characteristics together with pH and temperature independence of the sorption process make the mat biomass an ideal MB sorbent.     

Phycoremediation of lead and cadmium by employing Nostoc muscorum as biosorbent and optimization of its biosorption potential

The present study reports the influence of different factors on the sorption of Pb and Cd by Nostoc muscorum. The results showed that extent of Pb and Cd removal by N. muscorum cells increased with increasing biosorbent dose, but exhibited decline in the adsorption capacity. The maximum sorption of Cd (85.2%) and Pb (93.3%) was achieved at 60 and 80 μg/ml concentrations of respective metal, within 30 and 15 min, respectively. The result revealed that optimum biosorption of Pb and Cd occurred at pH 5 and 6, respectively, at 40°C temperature. Presence of binary metals (both Pb and Cd) in a solution showed that the presence of one metal ion resulted into decreased sorption of other metal ion. The presence of Ca and EDTA showed significant decrease in the sorption of Pb and Cd, while other anions and cations did not show significant effect on the biosorption of both the metals. Maximum desorption of Pb and Cd was achieved in the presence of EDTA and HNO₃, respectively. Results also showed that the test biosorbent could be repeatedly used up to six biosorption/desorption cycles without significant loss of its initial metal adsorption capacity.     

Thermodynamic Parameters of Ligand-Receptor Interactions: Computation and Error Margins

Abstract

A semiempirical relationship describing the temperature function of ligand-receptor dissociation constants (K_d), derived from heat capacities of the system in equilibrium, is suggested for computation of the standard enthalpy (δH°) and standard entropy (δS°) changes in equilibrium. The use of the linear expression (called Gibbs-van't Hoff equation) may lead to inaccurate results when heat capacity C_p displays a considerable temperature dependence. The accuracy of K_d, δH° and δS° has been studied by simulation experiments. In the case of K_d, deviations of computed from “true” values are determined by both the accuracy of experimental data used for its estimation, and by the shape of the binding isotherm (for instance, by Hill coefficients or by the presence of low affinity sites). As a rule, if errors of bound ligand measurements are greater than 20 per cent, K_d estimates ought to be considered as less reliable. However, computations of δH° and δS° that use such K_d values, are more correct, probably due to an error compensation. The suggested nonlinear temperature function of K_d enables an estimate of the heat capacity of the system and its temperature dependence.     

Sorption Behavior of Cesium in Two Greek Soils: Effects of Cs Initial Concentration,Clay Mineralogy,and Particle-size Fraction

The characteristics of Cs sorption behavior in two soils (soil 1 and soil 2) with nearly the same clay content and exhangeable K concentration, but with different clay mineralogy, were studied by the quantification of the distribution coefficient (k_d). It was observed that as the initial Cs concentration increased from 4 to 50 mg L^?1, the k_d values decreased in both soils, suggesting a progressive saturation of Cs available sorption sites. However, the presence of expansible 2:1 phyllosilicates minerals in the clay fraction of soil 2 maintained a high Cs sorption ability for this soil, even at high Cs concentrations. The experimental data were also fitted to the Freundlich isotherm and the results showed that parameters of the Freundlich equation could be used to estimate the degree of Cs sorption and the nature of the available sorption sites. For the studied soils, the k_f and the k_d values followed a similar trend and the n Freundlich constant values provided a reliable indicator for the soils’ clay mineralogy. The removal of the sand fraction enhanced Cs sorption in both soils and the absence of sorbed Cs ions on the quartz minerals, as observed by the SEM analysis, additionally supported the effect of particle-size fraction on Cs sorption.     

Norfloxacin Sorption to Different Fractions in Sediments from Typical Water Systems in China

Sorption isotherms of Norfloxacin (NOF) to different fractions from six typical sediments in China were determined to compare the NOF sorption behavior and contribution of different fractions to total sorption. All sorption isotherms were nonlinear and fitted well with the Freundlich model. Sorption coefficients (K _f) by original sediments changed in larger magnitude, from 114 (mg/g)/(mg/L)ⁿ to 5271 (mg/g)/(mg/L)ⁿ, and black carbon with more aromatic carbon has more sorption capacity and nonlinearity. The sorption capacity K _f values were found to significantly correlate with SSA (specific surface area), OC (organic carbon), BC (black carbon), and TON (total organic nitrogen) (p < 0.05), but had no obvious relation with pH, CEC (cation exchange capacity), TOC/TON, and BC/TOC. The DOC removed, NaOH extracted, and 375°C heated fractions showed more nonlinear sorption than the original sediments, suggesting more heterogeneous sorption sites in these fractions. Among different sediment fractions, the 375°C heating fractions were responsible for >50% of the total NOF sorption over the whole concentration range. The contribution of DOC removed fractions to the total sorption was the highest at higher NOF concentration.