A method for determining the phosphorus sorption capacity and amorphous aluminum of aluminum-based drinking water treatment residuals

A high amorphous aluminum or iron oxide content in drinking water treatment residuals (WTRs) can result in a high phosphorus (P) sorption capacity. Therefore, WTR may be used beneficially to adsorb P and reduce P loss to surface or ground water. The strong relationship between acid ammonium oxalate-extractable aluminum (Al(ox)) and Langmuir phosphorus adsorption maximum (P(max)) in WTR could provide a useful tool for determining P(max) without the onus of the multipoint batch equilibrations necessary for the Langmuir model. The objectives of this study were to evaluate and/or modify an acid ammonium oxalate extraction of Al(ox) and the experimental conditions used to generate P adsorption isotherms to strengthen the relationship between Al(ox) and P(max). The oxalate extraction solution to WTR ratio varied from 40:1, 100:1, and 200:1. Batch equilibration conditions were also varied. The WTR particle size was reduced from <2 mm to <150 microm, and batch equilibration was extended from 17 h to 6 d. Increasing the solution to WTR ratio to 100:1 extracted significantly greater Al(ox) at levels of >50 mg Al kg(-1). No additional increase was found at 200:1. Reducing WTR particle size from <2 mm to <150 microm increased P(max) 2.46-fold. Extending the equilibration time from 17 h to 6 d increased P(max) by a mean of 5.83-fold. The resulting empirical regression equation between the optimized Al(ox) and P(max) (r(2) = 0.91, significant at the 0.001 probability level) may provide a tool to estimate the P(max) of Al-based WTR simply by measuring Al(ox). The accurate determination of WTR P(max) and Al(ox) is essential in using WTR effectively to reduce P loss in runoff or to reduce the solubility of P in agricultural soils or organic waste materials (biosolids, manure).     

Oxytetracycline sorption to organic matter by metal-bridging

The sorption of oxytetracycline to metal-loaded ion exchange resin and to natural organic matter by the formation of ternary complexes between polyvalent metal cations and sorbent- and sorbate ligand groups was investigated. Oxytetracycline (OTC) sorption to Ca- and Cu-loaded Chelex-100 resin increased with increasing metal/sorbate ratio at pH 7.6 (OTC speciation: 55% zwitterion, 45% anion). Greater sorption to Cu- than Ca-loaded resin was observed, consistent with the greater stability constants of Cu with both the resin sites and with OTC. Oxytetracycline sorption to organic matter was measured at pH 5.5 (OTC speciation: 1% cation, 98% zwitterion, 1% anion). No detectable sorption was measured for cellulose or lignin sorbents that contain few metal-complexing ligand groups. Sorption to Aldrich humic acid increased from "clean" < "dirty" (no cation exchange pretreatment) < Al-amended < Fe(III)-amended clean humic acid with K(d) values of 5500, 32000, 48000, and 250000 L kg(-1) C, respectively. Calcium amendments of clean humic acid suggested that a portion of the sorbed OTC was interacting by cation exchange. Oxytetracycline sorption coefficients for all humic acid sorbents were well-correlated with the total sorbed Al-plus-Fe(III) concentrations (r(2) = 0.87, log-log plot), suggesting that sorption by ternary complex formation with humic acid is important. Results of this research indicate that organic matter may be an important sorbent phase in soils and sediments for pharmaceutical compounds that can complex metals by the formation of ternary complexes between organic matter ligand groups and pharmaceutical ligand groups.     

Phenanthrene sorption to structurally modified humic acids

Several studies emphasize the importance of soil organic matter characteristics in hydrophobic contaminant sorption and outline the strong dependence of sorption on organic matter aromaticity. In this study, the role of organic matter aromaticity in phenanthrene sorption was investigated using humic acids (HAs) from compost, peat, and soil that were structurally modified by bleaching, hydrolysis, oximation, and subcritical water extraction. The HAs were characterized with cross polarization magic angle spinning carbon-13 nuclear magnetic resonance (CPMAS 13C NMR) spectroscopy and used in batch equilibrations with phenanthrene. Bleaching substantially reduced the aromaticity of the samples whereas the other treatments increased the relative aromaticity. Phenanthrene sorption increased, even though there was a substantial reduction in sorbent aromaticity with some samples. The HAs that exhibited comparable CPMAS 13C NMR spectra and aromaticity did not behave similarly with respect to phenanthrene sorption. When the sorption data (K(oc) values) were correlated to sample aromaticity, the correlation coefficients (r2) did not exceed 0.39. Comparisons with the atomic H to C ratio provided slightly better r2 values (up to 0.54). This study demonstrates that macroscopic sorbent characteristics could not explain the observed phenanthrene sorption coefficients, aliphatic structural components of HAs can contribute appreciably to phenanthrene sorption, and organic matter physical conformation may regulate access to organic matter structures. Therefore, the use of only macroscopic sorbent properties, such as aromaticity, to predict and rationalize sorption values cannot solely be used to explain the behavior of organic contaminants in soil environments.     

A new method to quantify the impact of soil carbon management on biophysical soil properties: the example of two apple orchard systems in New Zealand

A new method to diagnose the environmental sustainability of specific orchard management practices was derived and tested. As a significant factor for soil quality, the soil carbon (C) management in the topsoil of the tree-row of an integrated and organic apple orchard was selected and compared. Soil C management was defined as land management practices that maintain or increase soil C. We analyzed the impact of the soil C management on biological (microbial biomass C, basal respiration, dehydrogenase activity, respiratory quotient) and physical (aggregate stability, amount of plant-available water, conductive mean pore diameter near water saturation) soil properties. Soil in the alley acted as a reference for the managed soil in the tree row. The total and hot-water-extractable C amounts served as a combined proxy for the soil C management. The soil C management accounted for 0 to 81% of the degradation or enhancement of biophysical soil properties in the integrated and organic system. In the integrated system, soil C management led to a loss of C in the top 0.3 m of the tree row within 12 yr, causing a decrease in microbial activities. In the tree row of the organic orchard, C loss occurred in the top 0.1 m, and the decrease in microbial activities was small or not significant. Regarding physical soil properties, the C loss in the integrated system led to a decrease of the aggregate stability, whereas it increased in the organic system. Generally, the impact of soil C management was better correlated with soil microbial than with the physical properties. With respect to environmental soil functions that are sensitive to the decrease in microbial activity or aggregate stability, soil C management was sustainable in the organic system but not in the integrated system.     

Validation of procedures to quantify nonextractable polycyclic aromatic hydrocarbon residues in soil

This study was conducted to optimize butanol solvent shake extraction, dichloromethane soxtec extraction, and methanolic saponification extraction for the selective extraction of aged polycyclic aromatic hydrocarbons from soil. Extraction kinetics for these methods was established to determine the optimal time necessary to achieve exhaustive compound extraction. This resulted in times of 12, 6, and 5 h, respectively, for butanol, dichloromethane, and saponification, to extract polycyclic aromatic hydrocarbons from previously spiked, then aged soil. Increasing the soil mass to butanol volume ratio reduced the proportion of polycyclic aromatic hydrocarbon extracted by butanol, highlighting the importance of determining and maintaining a constant soil to solvent ratio for comparative purposes. Drying soil samples before dichloromethane soxtec extraction reduced by 30 to 76% the amount of polycyclic aromatic hydrocarbons extracted. The effect of sample drying is discussed with relevance to enhancing the formation of nonextractable compounds in soil and compound losses previously assumed by volatilization. The optimized extraction procedures provided low variability with relative standard deviations < or = 5.2% for analysis of multiple replicates. The results obtained by the optimized procedures provided equivalent or improved reproducibility to those obtained by other methods reported in the literature.     

Use of alkaline extraction to quantify sulfate concentration in oxidized mine tailings

An alkaline extraction method has been developed for the determination of total sulfate in mine tailings containing secondary sulfate minerals formed by the oxidation of primary sulfides. Oxidized tailings were extracted with a 0.3 M NaOH solution at a liquid/solid ratio of 30 at room temperature for 16 h. The sulfate concentration in the extracts was determined by ion chromatography (IC). The coefficient of variation for sulfate determinations ranged from 1.9 to 3.2% for five tailings samples collected at two tailings impoundments. Mineralogical analysis of the tailings by scanning electron microscopy/X-ray energy dispersive spectrometry (SEM/EDS) demonstrated that the extraction of sulfate was complete, with the exception of extremely insoluble barite. The proposed method is simple, yields an accurate yet rapid measurement of sulfate, and involves a safer laboratory operation than conventional methods that make use of strong HCl acid solutions. Moreover, this method allows the specific measurement of sulfate in the extract, whereas conventional methods are generally limited to the measurement of total S by inductively coupled plasma atomic emission spectrometry (ICP-AES) due to the interference of chloride with sulfate in IC.     

Measuring sorption of hydrophilic organic compounds in soils by an unsaturated transient flow method

Determination of sorption of hydrophilic, weakly sorbing organic compounds in soil by conventional batch methods using a slurried suspension is often prone to considerable errors because small changes in the solution concentration on equilibration must be accurately determined. This difficulty is exacerbated for compounds susceptible to degradation, which also decreases the solution concentration. The objective of this study was to determine sorption of hydrophilic pesticides by applying an unsaturated transient flow method, which enables determination of sorption at sufficiently small solution to soil ratios. The method makes use of piston-like displacement of the antecedent solution in equilibrium with sorbed phase when pesticide-free water is infiltrated into a soil column spiked with a pesticide. Pesticide sorption and the solution concentration are inferred from a plot of total pesticide content per unit mass of soil vs. water content in a region where the antecedent solution is accumulated. Thus, extraction of solution from relative dry soil is unnecessary. We tested this method for two hydrophilic pesticides, monocrotophos [dimethyl (E)-1-methyl-2-(methyl-carbamoyl) vinyl phosphate] and dichlorvos (2,2-dichlorovinyl dimethyl phosphate). The sorption coefficient, K(d), obtained for monocrotophos was slightly lower than that by batch method (K(d) = 0.10 vs. 0.19 L kg(-1)), whereas for dichlorvos, a compound highly susceptible to degradation, the unsaturated flow method yielded a much smaller K(d) (0.19 vs. 3.22 L kg(-1)). The K(d) values for both compounds were consistent with the observed retardation in the pesticide displacement in the columns. The proposed method is more representative of field conditions and particularly suitable for weakly sorbing organic compounds in soils.     

Using nitrogen-15 to quantify vegetative buffer effectiveness for sequestering nitrogen in runoff

Previous studies have observed higher levels of soluble nutrients leaving vegetative buffers than entering them, suggesting that the buffers themselves are acting as a source rather than a sink by releasing previously stored nutrients. This study used 98 atom % (15)N-labeled KNO(3) at a rate of 5 kg ha(-1) to quantify buffer efficiency for sequestering new inputs of NO(-)(3)-N in an extensively grazed irrigated pasture system. Buffer treatments consisted of an 8-m buffer, a 16-m buffer, and a nonbuffered control. Regardless of the form of runoff N (NO(-)(3), NH(+)(4), or dissolved organic nitrogen [DON]), more (15)N was lost from the nonbuffered treatments than from the buffered treatments. The majority of the N attenuation was by vegetative uptake. Over the course of the study, the 8-m buffer decreased NO(-)(3)-(15)N load by 28% and the 16-m buffer decreased load by 42%. For NH(+)(4)-(15)N, the decrease was 34 and 48%, and for DON-(15)N, the decrease was 21 and 9%. Although the buffers were effective overall, the majority of the buffer impact occurred in the first four weeks after (15)N application, with the buffered plots attenuating nearly twice as much (15)N as the nonbuffered plots. For the remainder of the study, buffer effect was not as marked; there was a steady release of (15)N, particularly NO(-)(3)- and DON-(15)N, from the buffers into the runoff. This suggests that for buffers to be sustainable for N sequestration there is a need to manage buffer vegetation to maximize N demand and retention.     

A new way to use solid-state carbon-13 nuclear magnetic resonance spectroscopy to study the sorption of organic compounds to soil organic matter

Several solid-state 13C nuclear magnetic resonance (NMR) techniques were used to characterize soil organic matter spiked with 13C-labeled organic compounds spanning a range of hydrophobicities (benzoic acid, benzophenone, naphthalene, phenanthrene, and palmitic acid). The chemical shifts of NMR resonances of the sorbed species were shifted by up to 3 ppm relative to those of the neat compounds. Sorption also resulted in increased resonance linewidth for the compounds containing a single 13C label, indicating the presence of a range of different chemical environments at the sites of sorption. On the other hand, sorption decreased the linewidth of the resonance of naphthalene, which was uniformly 13C-labeled. This was attributed to the removal of intermolecular 13C-13C dipolar coupling. Heterogeneity of the organic matter was demonstrated using the spectral editing technique proton spin relaxation editing (PSRE), which enabled the identification and quantification of charcoal-rich domains characterized by rapid rates of proton spin-lattice relaxation in the static frame (T1H), and humic domains characterized by slow rates of T1H relaxation. Furthermore it was demonstrated that the sorbed 13C-labeled molecules "inherit" the T1H "signature" of the organic matrix in their immediate vicinity. Thus PSRE on the spiked soils enabled evaluation of the relative affinity of the two domain types for the sorbate molecules. The charcoal-rich domains were shown to have a twofold to tenfold greater affinity for the organic compounds, with greater differences found for the more hydrophobic compounds.     

Using nonequilibrium thin-disc and batch equilibrium techniques to evaluate herbicide sorption

Nonequilibrium disc-flow techniques may better reproduce dynamic soil-pesticide interactions than traditional batch sorption studies. Batch kinetic and equilibrium experiments and dual-label thin-disc flow experiments were conducted with atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazine-2,4-diamine) and imazaquin [2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-3-quinolinecarboxylic acid] using a Demopolis silt loam (loamy-skeletal, carbonatic, thermic, shallow Typic Udorthent; 8% clay, 62 g kg(-1) organic matter, 7.6 pH). Batch kinetic studies with both herbicides revealed an almost instantaneous rapid phase and a much slower gradual phase. The rapid phase was complete after 5 min and equilibrium was reached at 24 h. The rapid phase accounted for 74% and 12 to 30% of the total amounts adsorbed for atrazine and imazaquin, respectively. The sorption of both the rapid and 24-h isotherms for each herbicide best fit the Freundlich equation. The rapid and 24-h K(f) values of atrazine were 1.38 and 2.41, respectively, and the N value of both phases was approximately 0.93. For imazaquin, the rapid and 24-h K(f) values were 0.056 and 035, respectively, and the N value for the rapid phase of imazaquin was 0.71, compared with 0.86 for the 24-h isotherm. In the dual-label thin-disc flow experiments, the average partition coefficient for atrazine at the peak soil concentration point was 1.54. This value closely agreed with the observed rapid-phase K(f) value of 1.38. In contrast, the thin-disc flow experiments failed to detect any imazaquin retention. The thin-disc flow method can allow for a greater resolution of rapid sorption kinetics, which is impractical with batch studies. Along with dynamic partitioning data, the thin-disc flow method may provide kinetics data that may better complement environmental models than coefficients generated with batch techniques.     

A tradeoff method to assess housing location preferences

In public decision making, tradeoffs between competing goods must be made by someone other than the user. A tradeoff technique provides a means both to allow users to participate in the decision making process and to educate users about the constraints involved in making such decisions. Seventy-two female public housing tenants were asked to describe their ideal housing location in terms of 20 attributes, including preferred distance to 16 facilities and preferred quality of four features of the environment. In the tradeoff situation, they were given constrained budgets and asked to ‘buy’ the most satisfactory location based on these 20 attributes. The ideal and tradeoff approaches show a general agreement about attributes that should be most heavily weighted in making decisions about public housing location. The rank order of the importance of the attributes differs, however, indicating that the tradeoff method should be used to weight the importance of each attribute. Residents' responses were influenced by the availability of an automobile but were relatively little affected by the personal characteristics of race, age of children and employment status.     

Revisiting a statistical shortcoming when fitting the Langmuir model to sorption data

The Langmuir model is commonly used for describing the sorption behavior of reactive solutes to surfaces and is often fit to sorption data using nonlinear least squares regression. An important assumption of least squares regression is that the predictor variable is error free. In the case of sorption data, this assumption is not valid, and therefore the potential for parameter bias exists. Although alternative regression methods exist that either explicitly account for error in the predictor variable (Model II regression) or minimize the error in the predictor variable, these methods are not commonly used. Therefore, this paper more fully explores the differences in fitted parameters and model fits between these different data fitting methods by fitting P sorption data collected on 26 different soil samples using three different regression methods. For a majority of soils tested in this study, the differences in model fits between the three regression methods were not statistically significant. Statistical differences were observed in over a third of the soils, however, suggesting that errors in the predictor variable may be large enough to produce biased parameter estimates. These results suggest that multiple regression methods should be used when fitting the Langmuir model to sorption data to better assess the potential impact of error on model fits.     

Regeneration of spent organoclays after the sorption of organic pollutants: A review

Clay minerals modified with organic ions, also known as organoclays, have found applications in a wide range of organic pollution control fields because of their excellent sorption capacity towards organic pollutants. Regeneration of the spent organoclays after the sorption of organic pollutants is of great importance during their application in pollution control. In this review, the reported methods for the regeneration of the spent organoclays are summarized, including biological degradation, photo-assisted oxidation, chemical extraction/desorption, supercritical extraction, thermal desorption, et al. The characteristics and applications of these methods are briefly described. It shows that most of these methods have been developed for regenerating spent organoclays from wastewater treatment. The biological regeneration method, as an in situ, low cost and easy-operating method, is applicable for regenerating spent organoclays not only from wastewater treatment, but also from soil and groundwater remediation.     

A novel method to make regenerable core-shell calcium-based sorbents

A sorbent having a calcium oxide core and a clay shell was prepared and shown to be capable of reusable applications in absorption and desorption processes for carbon dioxide. The novelty of this sorbent is that only calcium carbonate and clay are used for its preparation with water as a binder. A two-step granulation procedure is used to get the core and then another step to coat the shell layer with the clay powder. A repeated wet-and-dry procedure probably makes the core porous yet strong enough to serve as a sorbent. The pellet is then calcined at 1200 degrees C for 2h to reach its final structure. The core-shell pellets have an overall diameter of 4.4mm with average shell thickness of 0.45 mm, crush load of 35 N and attrition index of 0.035 wt%/h. These results indicate that the pellets will probably be capable of withstanding the stress in future applications. Carbon dioxide absorption at or below 300 degrees C showed a maximum weight gain of 38% for our pellets. Finally, desorption in nitrogen at 800 degrees C can restore the pellet to its original state and hence it is ready for re-use as a sorbent.     

Using surfactant-modified clays to determine sorption mechanisms for a representative organic base, quinoline

Sorption of a representative ionizable nitrogen heterocycle, quinoline (pKa = 4.92), was investigated to determine the relative contributions of the neutral and protonated species to the overall process. Batch sorption experiments were conducted on surfactant-modified clays that were synthesized from the exchange of hexadecyltrimethylammonium cations for resident sodium cations on a specimen smectite (Swy-2) at 0, 60, 80, and 100% of the clay's cation exchange capacity (CEC). Hexadecyltrimethylammonium exchange creates highly effective organic partitioning domains within the clay interlayers in proportion to their coverage on the exchange complex. The fractionally exchanged clays, therefore, provided discrete exchange and organic partitioning domains for the protonated and neutral species of quinoline. Data were described by a combined Langmuir-linear isotherm that permitted independent characterization of both sorption components. Results indicated that cationic sorption dominated but that the neutral species can contribute substantially given sufficient organic carbon content relative to the CEC and at pH above the pKa of quinoline. The data obtained in this study for quinoline demonstrated that the combined isotherm (including cation exchange and hydrophobic partitioning terms) describes sorption data and compares favorably with the purely empirical Freundlish isotherm.     

A spatially explicit investigation of phosphorus sorption and related soil properties in two riparian wetlands

Soils of riparian wetlands are highly effective at phosphorus (P) sorption. However, these soils exhibit extreme spatial variability across riparian zones. We used a spatially explicit sampling design in two riparian wetlands in North Carolina to better understand the relationships among P sorption, soil properties, and spatial variability. Our objectives were to quantify patterns of spatial variability of P sorption and related soil properties, and to determine which soil properties best explained the variability in P sorption after accounting for the effects of spatial autocorrelation. We measured bulk density, moisture, pH, soil organic matter (SOM), texture (percent clay, silt, and sand), oxalate-extractable aluminum (Al(ox)), iron (Fe(ox)), and the phosphorus sorption index (PSI). Due to differences in texture, Al(ox), and Fe(ox), the two sites had substantially different mean PSIs. At each site, we found considerable differences in the spatial variability of soil properties. For example, semivariance analysis and kriging illustrated that soil properties at Site 1 varied at smaller scales than those at Site 2. At both sites, after accounting for the effects of spatial autocorrelation and all other soil properties, we determined that Al(ox) had the highest Mantel correlation with PSI. We believe this geostatistic and Mantel approach is robust and could serve as a model for research on other biogeochemical processes such as denitrification.     

Herbicide sorption coefficients in relation to soil properties and terrain attributes on a cultivated prairie

The sorption of 2,4-D and glyphosate herbicides in soil was quantified for 287 surface soils (0-15 cm) collected in a 10 x 10 m grid across a heavily eroded, undulating, calcareous prairie landscape. Other variables that were determined included soil carbonate content, soil pH, soil organic carbon content (SOC), soil texture, soil loss or gain by tillage and water erosion, and selected terrain attributes and landform segments. The 2,4-D sorption coefficient (Kd) was significantly associated with soil carbonate content (-0.66; P < 0.001), soil pH (-0.63; P < 0.001), and SOC (0.47; P < 0.001). Upper slopes were strongly eroded and thus had a significantly greater soil carbonate content and less SOC compared with lower slopes that were in soil accumulation zones. The 2,4-D Kd was almost twice as small in upper slopes than in lower slopes. The 2,4-D Kd was also significantly associated with nine terrain attributes, particularly with compounded topographic index (0.59; P < 0.001), gradient (-0.48; P < 0.001), mean curvature (-0.43; P < 0.001), and plan curvature (-0.42 P < 0.001). Regression equations were generated to estimate herbicide sorption in soils. The predicted power of these equations increased for 2,4-D when selected terrain attributes were combined with soil properties. In contrast, the variation of glyphosate sorption across the field was much less dependent on our measured soil properties and calculated terrain attributes. We conclude that the integration of terrain attributes or landform segments in pesticide fate modeling is more advantageous for herbicides such as 2,4-D, whose sorption to soil is weak and influenced by subtle changes in soil properties, than for herbicides such as glyphosate that are strongly bound to soil regardless of soil properties.     

Phosphorus and nitrogen sorption to soils in the presence of poultry litter-derived dissolved organic matter

Two environmental aspects associated with land application of poultry litter that have not been comprehensively evaluated are (i) the competition of dissolved organic matter (DOM) and P for soil sorption sites, and (ii) the sorption of dissolved organic nitrogen (DON) relative to inorganic nitrogen species (e.g., NO(3)(-) and NH(4)(+)) and dissolved organic carbon (DOC). The competition between DOM and P for sorption sites has often been assumed to increase the amount of P available for plant growth; however, elevating DOM concentrations may also increase P available for transport to water resources. Batch sorption experiments were conducted to (i) evaluate soil properties governing P sorption to benchmark soils of Southwestern Missouri, (ii) elucidate the impact of poultry litter-derived DOM on P sorption, and (iii) investigate DON retention relative to inorganic N species and DOC. Soils were reacted for 24 h with inorganic P (0-60 mg L(-1)) in the presence and absence of DOM (145 mg C L(-1)) using a background electrolyte solution comparable to DOM extracts (I = 10.8 mmol L(-1); pH 7.7). Soil P sorption was positively correlated with metal oxide (r(2) = 0.70) and clay content (r(2) = 0.79) and negatively correlated with Bray-1 extractable P (r(2) = 0.79). Poultry litter-derived DOM had no significant negative impact on P sorption. Dissolved organic nitrogen was preferentially removed from solution relative to (NO(3)(-)-N + NO(2)(-)-N), NH(4)(+)-N, and DOC. This research indicates that poultry litter-derived DOM is not likely to enhance inorganic P transport which contradicts the assumption that DOM released from organic wastes increases plant-available P when organic amendments and fertilizer P are co-applied. Additionally, this work demonstrates the need to further evaluate the fate and transport of DON in agroecosystem soils receiving poultry litter applications.     

Effect of heat treatment on sorption of polar and nonpolar compounds to montmorillonites and soils

Batch sorption isotherms of 1,3,5-trichlorobenzene, 1,3,5-trinitrobenzene, and tetracycline to organic-free montmorillonites and soils receiving heat treatment (375°C for 24 h) were compared with those to unheated sorbents. Sorption of the nonpolar 1,3,5-trichlorobenzene to soil was lowered after the removal of humus by heating, consistent with the mechanism of hydrophobic partition into organic matter. For 1,3,5-trinitrobenzene, the enhanced sorption to heated soils was attributed to specific interactions with exchangeable cations facilitated by heating-induced irreversible partial dehydration of the clay interlayer. For tetracycline, an additional mechanism for sorption enhancement could be due to increased exposure of strong complexation sites on clay minerals after removal of the humic coating. These hypotheses were supported by the sorption data to heated and unheated Na-, K-, and Cs-saturated montmorillonites. The combustion method is commonly adopted to measure the content of black carbon in soils and sediments. However, findings from the present study indicate that combustion may greatly modify the structural properties of clay minerals, leading to misinterpreted sorption contributions of different soil components to sorption of polar or ionic compounds.     

Molecular-level investigation of monoaromatic compound sorption to suspended soil particles by deuterium nuclear magnetic resonance

Molecular-level sorption behavior of monoaromatic compounds in suspensions of water-dispersable clay components was studied by measuring 2H nuclear magnetic resonance (NMR) spin-spin relaxation times (T2). In general, decreased T2 values indicate stronger solute-sorbent interactions and increased sorption of the solute. A decreasing trend for T2 values in the order benzene > fluorobenzene > toluene (-C6D5 moiety) was observed, which was probably caused by the hydrophobic effect. The T2 values for benzene and the -C6D5 moiety of toluene increased with increasing pH, whereas the trend with pH was much weaker and less consistent for fluorobenzene and the methyl group of toluene. Conversely, no clear relationship was found between T2 values and pH for dichloromethane. These contrasting results cannot be explained by the pH-dependent self-assembly and hydrophobicity of humics. Instead, directed specific forces, including hydrogen bonding, cation-pi interactions, and aromatic-aromatic interactions, are proposed between the benzene ring of monoaromatic solutes and soil organic matter (SOM). Substituents of benzene affect these interactions by varying the pi electron density. When the soil fraction was treated with NaOH to remove humic and fulvic acids, T2 values for the different monoaromatic solutes were surprisingly lower compared with those for the untreated soil fraction. This result is probably caused by the increased ratio of solutes adsorbed to "hard" or "glassy" SOM components, which leads to less mobile sorbed solute molecules, after removing NaOH-extractable humics that contain more "soft" or "rubbery" SOM components.