Sorption of naphthalene and phenanthrene by soil humic acids

Humic acids are a major fraction of soil organic matter (SOM), and sorption of hydrophobic organic chemicals by humic acids influences their behavior and fate in soil. A clear understanding of the sorption of organic chemicals by humic acids will help to determine their sorptive mechanisms in SOM and soil. In this paper, we determined the sorption of two hydrophobic organic compounds, naphthalene and phenanthrene by six pedogenetically related humic acids. These humic acids were extracted from different depths of a single soil profile and characterized by solid-state CP/MAS 13C nuclear magnetic resonance (NMR). Aromaticity of the humic acids increased with soil depth. Similarly, atomic ratios of C/H and C/O also increased with depth (from organic to mineral horizons). All isotherms were nonlinear. Freundlich exponents (N) ranged from 0.87 to 0.95 for naphthalene and from 0.86 to 0.92 for phenanthrene. The N values of phenanthrene were consistently lower than naphthalene for a given humic acid. For both compounds, N values decreased with increasing aromaticity of the humic acids, such an inverse relationship was never reported before. These results support the dual-mode sorption model where partitioning occurs in both expanded (flexible) and condensed (rigid) domains while nonlinear sorption only in condensed domains of SOM. Sorption in the condensed domains may be a cause for slow desorption, and reduced availability and toxicity with aging.     

Retention of organic and inorganic chemicals by the drainage/supply piping material

A critical issue facing the turfgrass industry is the environmental fate and transport of organic and inorganic chemicals used on golf courses. The fate and distribution of those chemicals are strongly influenced by sorptive interactions with soil and sediment. In this study, the drainage and water supply piping material (used for construction of a prototype encapsulated golf green) was utilized to determine its potential sorption of three organic chemicals [2,4-dichloro-phenoxyacetic acid] (2,4-D), naphthalene and toluene and nitrate. Crushed piping material (small-to-large particle sizes) was evaluated. Isotherms were constructed using a batch equilibration technique. The results showed that the drainage/supply piping material at small particle sizes (<2.5 mm) has higher sorptive ability compared to soil (1.7 for 2,4-D and 13.4 for naphthalene). The K(F) value was 44, 253 and 70 for 2,4-D, naphthalene and toluene, respectively. K(oc) values were much higher than those of peat and soil at lower equilibrium concentrations. However, sorption decreased dramatically with increasing particle size (approaching zero at particle size 10 mm), due to reduction of surface areas and sorption sites. Sorption of NO(3)-N by the piping material was negligible. We concluded that sorption by intact drainage/supply piping material would not affect the recycling efficiency of pesticides and nutrients in the constructed encapsulated green. Conversely, drainage/supply piping material particles smaller than 2.5 mm in diameter can effectively be utilized as a filtering material.     

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.     

Sorption of naphthalene derivatives to soils from a long-term field experiment

The influence of long-term farming practices on the soil's behaviour to adsorb hydrophobic organic compounds (HOCs) over long times was investigated. Adsorption of five naphthalene derivatives (naphthalene, 1-naphthol, 1-naphthylamine, 1-hydroxy-2-naphthoic acid, 1,4-naphthoquinone) was examined on soils with varying amounts and origins of soil organic matter obtained after amendment with different organic materials over more than 40 years. Soil organic matter, pore sizes and aggregate stability were significantly altered influencing the adsorption behaviour of the soils. Samples of soil amended with peat having an organic carbon content of 3.4% sorbed naphthalene derivatives stronger than the soil treated with sewage sludge (2.6% C(org)). All other treatments, calcium nitrate, plots without nitrogen fertilizers, grassland, animal manure, green manure and the fallowed soil sorbed less and no significant difference was found between them although the organic carbon content ranged from 1.0% to 2.6%. Thus, a decrease of the carbon content of a soil does not necessarily imply a reduction of sorption capacities for hydrophobic compounds such as naphthalene derivatives. Furthermore, the importance of protonation of HOCs for the adsorption on soil surfaces was shown. Different polarities of electronic structures of HOCs distinctly influence their adsorption behaviour.     

The equilibria of bisolute sorption on soil

The goal of this study was to investigate the effects of both concentration levels and loading sequence or contamination history of each pollutant on the equilibrium sorption of mixed organic pollutants on soils. We measured binary sorption equilibria for a soil using ten concentration levels for both phenanthrene and naphthalene. Both solutes were either simultaneously loaded or sequentially loaded (i.e., the second sorbate was loaded after the sorption of the first sorbate had attained equilibrium) on soil. The results showed different competitive sorption equilibria between phenanthrene and naphthalene. In the presence of phenanthrene and regardless of loading sequence, naphthalene exhibited consistently lower sorption capacities and the ideal adsorbed solution theory (IAST) slightly underestimates the naphthalene sorption equilibria. Conversely, the sorption equilibria of phenanthrene in the presence of naphthalene depended upon the loading sequence of the two sorbates on the soil. Little competition from naphthalene on the sorption equilibria of phenanthrene was observed when phenanthrene was loaded either simultaneously with or sequentially after naphthalene, but appreciable competition from naphthalene was observed when the soil had been pre-contaminated with phenanthrene. IAST slightly underestimates the phenanthrene sorption equilibria observed in the latter system, but it cannot estimate the phenanthrene sorption equilibria in the former two systems. We proposed that adsorption on internal surfaces of ink-bottle shaped pores within relatively flexible sorbent matrix may have caused the competitive sorption phenomena observed in this study. The study suggests that contamination history may have strong influence on the equilibrium sorption of organic pollutant mixtures.     

Sorption of phenanthrene by soils contaminated with heavy metals

The fate of polycyclic aromatic hydrocarbons (PAHs) in soils with co-contaminants of heavy metals has yet to be elucidated. This study examined sorption of phenanthrene as a representative of PAHs by three soils contaminated with Pb, Zn or Cu. Phenanthrene sorption was clearly higher after the addition of heavy metals. The distribution coefficient (K(d)) and the organic carbon-normalized distribution coefficient (K(oc)) for phenanthrene sorption by soils spiked with Pb, Zn or Cu (0-1000 mg kg(-1)) were approximately 24% larger than those by unspiked ones, and the higher contents of heavy metals added into soils resulted in the larger K(d) and K(oc) values. The enhanced sorption of phenanthrene in the case of heavy metal-contaminated soils could be ascribed to the decreased dissolved organic matter (DOM) in solution and increased soil organic matter (SOM) as a consequence of DOM sorption onto soil solids. Concentrations of DOM in equilibrium solution for phenanthrene sorption were lower in the case of the heavy metal-spiked than unspiked soils. However, the decreased DOM in solution contributed little to the enhanced sorption of phenanthrene in the presence of metals. On the other hand, the sorbed DOM on soil solids after the addition of heavy metals in soils was found to be much more reactive and have far stronger capacity of phenanthrene uptake than the inherent SOM. The distribution coefficients of phenanthrene between water and the sorbed DOM on soil solids (K(ph/soc)) were about 2-3 magnitude larger than K(d) between water and inherent SOM, which may be the dominant mechanism of the enhanced sorption of phenanthrene by soils with the addition of heavy metals.     

Effect of lead on the sorption of 2,4,6-trichlorophenol on soil and peat

The effect of lead on the sorption of 2,4,6-trichlorophenol (2,4,6-TCP) on soil and peat was investigated using a batch equilibration method. Lead markedly diminished the sorption of 2,4,6-TCP, and 2,4,6-TCP had little effect on lead sorption. Peat was a more effective adsorbent for 2,4,6-TCP than soil. The desorption hysteresis of 2,4,6-TCP verified the presence of high-energy sorption sites. Mechanisms of lead suppression effect on the 2,4,6-TCP sorption included the following: Firstly, lead accelerated the aggregation of colloids, the aggregates covered the surface in part and shrunk the pore sizes of the adsorbents, hence decreased the sorption of 2,4,6-TCP. Secondly, X-ray absorption and Fourier transform infrared spectroscopy study suggested that lead competed with 2,4,6-TCP for carboxylic, phenolic and Si-OH groups of organic matter and clay minerals. Such competition was partly responsible for the overall suppression effect of lead on the sorption of 2,4,6-TCP.     

Ground discarded tires remove naphthalene, toluene, and mercury from water

Ground discarded tires adsorb naphthalene, toluene, and mercury ions (Hg2+) from aqueous solutions. Their sorption properties and kinetics were determined by batch equilibration techniques at 20 degrees C. The isotherms were linear for naphthalene and toluene and their sorption coefficients were about 1340 and 255 (ml/g), respectively. Sorption of the organic compounds by the ground rubber particles was relatively fast (within 30 min). However, the mercury isotherms were non-linear, and its sorption was slow as compared to the sorption of the organics. The rubber particles had a strong affinity for Hg2+. These results show that ground discarded tires are effective in removing organic compounds and Hg2+ from wastewater and other contaminated environments. In addition it would be a useful, environmentally friendly use of discarded tires (one tire per year per capita is discarded in the United States).     

泥炭对甲苯的吸附-解吸行为研究

用热处理方法对泥炭进行活化改性,探讨了对甲苯的吸附性能及影响因素,并研究了甲苯在泥炭上的吸附/解吸行为。结果表明,粒径在0.6～1 mm之间的泥炭在160℃热处理5 h,在pH为7的条件下对甲苯有良好的吸附效果,对甲苯的吸附量为0.32 mg/g。泥炭对甲苯的吸附在20 min内基本达到平衡,可用二级吸附速率方程进行拟合。甲苯在泥炭上的吸附和解吸均呈现明显的非线性,用Langmuir模型能较好地描述,泥炭对甲苯的饱和吸附量为0.939 mg/g。甲苯在泥炭上的平均解吸率为6.393%,并且出现了滞后现象,表明苯系物与泥炭有较强的结合能力。研究结果为应用泥炭作为PRB装填介质进行原位修复甲苯污染的地下水提供了理论依据。     

Adsorptive removal of naphthalene induced by structurally different Gemini surfactants in a soil-water system

A new generation of surfactant, Gemini surfactants, have been synthesized and have attracted the attention of various industrial and academic research groups. This study focused on the use of symmetric and dissymmetric quaternary ammonium Gemini surfactants to immobilize naphthalene onto soil particles, and is used as an example of an innovative application to remove HOC in situ using the surfactant-enhanced sorption zone. The sorption capacity of modified soils by Gemini surfactant and natural soils was compared and the naphthalene sorption efficiency, in the absence and presence of Gemini surfactants with different alkyl chain lengths, was investigated in the soil-water system. The results have shown that the increased added Gemini surfactant formed admicelles at the interface of soil/water having superior capability to retard contaminant. Symmetric and dissymmetric Gemini surfactants have opposite effect on the aspect of removing of PAH attributing to their solubilization and sorption behavior in soil-water system. Compared with the natural soil, sorption of naphthalene by Gemini-modified soil is noticeably enhanced following the order of C_12-2-16 < C_12-2-12 < C_12-2-8. However, the symmetric Gemini surfactant C_12-2-12 is the optimized one for in situ barrier remediation, which is not only has relative high retention ability but also low dosage.     

Influences of preparative methods of humic acids on the sorption of 2,4,6-trichlorophenol

Humic acids (HAs) are a major component of soil organic matter which strongly affects the sorption behavior of organic contaminants in soils. To assess the sorption-desorption characteristics of organic compounds on HAs, the organic adsorbent is usually isolated using an acid-base extraction method followed by air-drying or freeze-drying. In this study, a peat soil from the Yangming mountain area of Taiwan was sampled and repeatedly extracted followed by either air-drying or a non-drying treatment (denoted DHAs and NDHAs, respectively). The sorption of 2,4,6-TCP on HAs was evaluated using the batch method. Kinetic sorption results indicated that DHAs exhibited a two-step first-order sorption behavior, involving a rapid sorption followed by a slow sorption. The slow sorption may be attributed to the diffusion of 2,4,6-TCP through the condensed aromatic domains of HAs. On the contrary, the sorption of 2,4,6-TCP on NDHAs was extremely rapid, and the sorption data did not fit existing kinetic models. Each HA sample exhibited a nonlinear sorption isotherm. Sorption nonlinearity (represented by Freundlich N values) and K(oc) had a positive relationship with aliphaticity for DHAs; however, nonlinearity and K(oc) correlated positively with aromaticity when NDHAs adsorbents were used. We conclude that the air-drying technique may artificially create a more condensed area, which strongly affects the sorption characteristics of HAs. Thus, an incorrect evaluation of the sorption capacity and its relationship with the chemical composition of HAs would arise following use of the air-drying method.     

Atrazine sorption by hydroxy-interlayered clays and their organic complexes

This study examined the sorption of atrazine by hydroxy-Fe interlayered montmorillonite (FeMt) and its hydroquinone (FeMtHQ), citrate (FeMtCt) and catechol (FeMtCC) complexes as well as by hydroxy-Al interlayered montmorillonite (AlMt) and its hydroquinone (AlMtHQ) and citrate (AlMtCt) complexes. Found among the clays were sorption distribution coefficients (K(d)) ranging from 24 to 123 mL g(-1) and maximum sorption (M) ranging from 2.2 to 16.8 microg g(-1). Both K(d) and M decreased in the order of FeMtCC > FeMtHQ > AlMtHQ > (AlMt = FeMt) > (AlMtCt = FeMtCt). The pH was negatively correlated with both K(d) (r = -0.90, p < 0.001) and M (r = -0.81, p < 0.001). When interlayered clays were associated with humified material (FeMtCC, FeMtHQ, AlMtHQ), both K(d) (r > 0.96, p < 0.01) and M (r > 0.94, p < 0.01) were highly positively correlated with total organic C and alkali-soluble C. However, clays with non-humified organic compounds (FeMtCt and AlMtCt) sorbed less atrazine than clays without any organic C (FeMt and AlMt). This suggests that functional groups of Fe-OH and Al-OH in FeMt and AlMt reduced the available sorption sites for atrazine by making complexes with citrate ions while forming FeMtCt and AlMtCt. The atrazine was sorbed through the hydrophobic interactions with organic compound surfaces as well as through H-bonding and ionic bonding with clay-mineral surfaces.     

Correlations of nonlinear sorption of organic solutes with soil/sediment physicochemical properties

The estimation of solute sorptive behaviors is essential when direct sorption data are unavailable and will provide a convenient way to assess the fate and the biological activity of organic solutes in soil/sediment environments. In this study, the sorption of 2,4-dichlorophenol (2,4-DCP) on 19 soil/sediment samples and the sorption of 13 organic solutes on one sediment were investigated. All sorption isotherms are nonlinear and can be described satisfactorily by a simple dual-mode model (DMM): q(e)=KpCe+Q0 . bCe/(1+bCe), where Kp (mlg(-1)) is the partition coefficient; Ce (microgml(-1)) is the equilibrium concentration; Q0 (microgg(-1)) is the maximum adsorption capacity; Q0 . b (mlg(-1)) is the Langmuir-type isotherm slope in the low concentration (Henry's law) range and b (mlmicrog(-1)) is a constant related to the affinity of the surface for the solute. Based on these nonlinear sorption isotherms and similar other nonlinear isotherms, it is observed that, for both polar 2,4-DCP and nonpolar phenanthrene, Kp, Q0 and Q0 . b are linearly correlated with soil/sediment organic carbon content (f(oc) in the range of 0.118-53.7%). The results indicate that the nonlinear sorption of organic solutes results primarily from interactions with soil/sediment organic matter. The K*oc K*oc=Kp/f(oc)), Qoc (Qoc=Q0/f(oc)), Loc (Loc=Q0 . b/f(oc)) and b for a given organic solute with different soils/sediments are largely invariant. Furthermore, logK*oc, logb and logLoc for various organic solutes are correlated significantly with the solute logKow or logSw (logKow in the range of 0.9 to 5.13 and logSw in the range of -6.176 to -0.070). A fundamental empirical equation was then established to calculate approximately the nonlinear sorption from soil/sediment f(oc) and solute Sw for a given solute equilibrium concentration.     

Kinetics and isotherm modeling of azoxystrobin and imidacloprid retention in biomixtures

The paper reports the kinetics and adsorption isotherm modeling for imidacloprid (IMIDA) and azoxystrobin (AZOXY) in rice straw (RS)/corn cob (CC) and peat (P)/compost (C) based biomixtures. The pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich and intraparticle diffusion models were used to describe the kinetics. The adsorption data were subjected to the Langmuir and the Freundlich isotherms. Results (r²_Adj values) suggested that the modified Elovich model was the best suited to explain the kinetics of IMIDA sorption while different models explained AZOXY sorption kinetics in different biomixtures (PFO in RS?+?C and RS?+?P; PSO in CC?+?P and Elovich in CC?+?C). Biomixtures varied in their capacity to adsorb both pesticides and the adsorption coefficient (K_d) values were 116.8–369.24 (AZOXY) and 24.2–293.4 (IMIDA). The Freundlich isotherm better explained the sorption of both pesticides. Comparison analysis of linear and nonlinear method for estimating the Freundlich adsorption constants was made. In general, r²_Adj values were higher for the nonlinear fit (AZOXY?=?0.938–0.982; IMIDA?=?0.91–0.970) than the linear fit (AZOXY?=?0.886–0.993; IMIDA?=?0.870–0.974) suggesting that the nonlinear Freundlich equation better explained the sorption. The rice straw-based biomixtures performed better in adsorbing both the pesticides and can be used in bio-purification systems.     

Leaching of mercury from peat soil

The factors influencing the sorption and leaching of mercury in peat soil were studied using small additions of labelled mercury in peat lysimeters. Additions of chloride, fertilizer or sterilant did not affect the leaching of mercury. Complete drying of the peat improved the leaching of mercury probably because of changes in the physical properties of the peat soil.     

Phenanthrene partitioning in sediment–surfactant–fresh/saline water systems

The objective of this study was to investigate the influence of salinity on the effectiveness of surfactants in the remediation of sediments contaminated with phenanthrene (PHE). This is an example of a more general application of surfactants in removing hydrophobic organic compounds (HOCs) from contaminated soil/sediment in saline environments via in-situ enhanced sorption or ex-situ soil washing. Salinity effects on surfactant micelle formation and PHE partitioning into solution surfactant micelles and sorbed surfactant were investigated. The critical micelle concentration of surfactants decreased, and PHE partition between surfactant micelles and water increased with increasing salinity. Carbon-normalized partition coefficients (K_ss) of PHE onto the sorbed cationic surfactant increased significantly with increasing salinity, which illustrates a more pronounced immobilization of PHE by cationic surfactant in a saline system. Reduction of PHE sorption by anionic surfactant was more pronounced in the saline system, indicating that the anionic surfactant has a higher soil washing effectiveness in saline systems.     

Sorption of organic contaminants by biopolymers: role of polarity, structure and domain spatial arrangement

Sorption behavior of hydrophobic organic contaminants (HOCs) (i.e., pyrene, phenanthrene and naphthalene) by native and chemically modified biopolymers (lignin, chitin and cellulose) was examined. Lignins (native and treated) showed nonlinear sorption for all compounds studied, emphasizing their glassy character. Chitins and celluloses had linear isotherms for phenanthrene and naphthalene, illustrating the dominance of partitioning, while pyrene yielded nonlinear isotherms. Sorption capacity (K(oc)) of HOCs was negatively correlated with the polarity [(O+N)/C] of the biopolymers. Aromatic and alkyl+aromatic C percentages, rather than alkyl C content, demonstrated a better correlation with K(oc) values, indicating the importance of aromatic structures for HOC affinity. Hydrophobicity (K(ow))-normalized K(oc) values decreased sharply with increasing percentage of O-alkyl C versus total aliphatic C (O-alkyl C/total aliphatic C) or with polar C/(alkyl+aromatic C) ratio of the biopolymers until their values reached 80% and 4, respectively, illustrating the effect of surrounding polar groups on reducing affinity for HOCs. Overall, the results of this study highlight the role of spatial arrangement of domains within biopolymers in sorption of HOCs, and point to sorbent properties, such as functionality, polarity and structure, jointly regulating the sorption of HOCs in biopolymers.     

Effect of lipids on sorption/desorption hysteresis in natural organic matter

The chemical composition and physical conformation of natural organic matter (NOM) play a major role in regulating its capacity to retain hydrophobic organic compounds. Naphthalene and phenanthrene were used to study the correlations between sorption/desorption isotherm nonlinearity and compositional data obtained from quantitative ¹³C solid-state DPMAS NMR spectroscopy for soil and peat organic matter with or without lipids. Sorption experiments were conducted using a batch equilibration method. Desorption experiments were carried out immediately following the sorption experiments by three successive decant-refill cycles. Hysteresis was observed in all samples. Nonlinear sorption behavior was increased by removal of lipids from the NOM. The hysteresis index, obtained from the ratio of the Freundlich exponents (N values) for the desorption and sorption isotherms, was lower in the lipid-extracted NOM samples than in the same samples without lipid extraction. The relationship between the extent of hysteresis and the characteristics of the ¹³C DPMAS NMR spectra indicates that altering NOM composition through lipid extraction not only increased the proportion of aromatic-C content, but also increased sorption/desorption hysteresis. Our data also suggest that the hysteresis index is negatively related to aromaticity.     

Distribution and speciation of mercury in the peat bog of Xiaoxing'an Mountain,northeastern China

Most reports on mercury (Hg) in boreal ecosystems are from the Nordic countries and North America. Comparatively little information is available on Hg in wetlands in China. We present here a study on Hg in the Tangwang River forested catchment of the Xiaoxing'an Mountain in the northeast of China. The average total Hg (THg) in peat profile ranged from 65.8 to 186.6 ng g(-1) dry wt with the highest at the depth of 5-10 cm. THg in the peat surface was higher than the background in Heilongjiang province, the Florida Everglades, and Birkeness in Sweden. MethylHg (MeHg) concentration ranged from 0.16 to 1.86 ng g(-1) dry wt, with the highest amount at 10-15 cm depth. MeHg content was 0.2-1.2% of THg. THg and MeHg all decreased with the depth. THg in upland layer of soil (0-20 cm) was comparable to the peat surface, but in deeper layers THg concentration in peat was much higher than that in the forested mineral soil. THg in the peat bog increased, but MeHg decreased after it was drained. THg content in plant was different; THg contents in moss (119 ng g(-1) dry wt, n=12) were much higher than in the herbage, the arbor, and the shrubs. The peat bog has mainly been contaminated by Hg deposition from the atmosphere.     

Effects of added PAHs and precipitated humic acid coatings on phenanthrene sorption to environmental Black carbon

Black carbon (BC; soot and charcoal) can be an extremely strong sorbent for organic compounds. In a previous study, sorption of d(10)-phenanthrene (d(10)-PHE) to BC in an unmodified contaminated sediment was found to be nine times less than that for BC isolated from this sediment. To find out the mechanism of this sorption attenuation (competition for BC sites between d(10)-PHE and native PAHs or blocking of BC sites by natural organic matter), we determined the effect on d(10)-PHE-BC sorption isotherms of additions of either PAHs or precipitated humic acid. Addition of humic acid did not significantly decrease BC sorption, whereas PAH additions (equal to the native PAH content in the original sediment) did, by about one order of magnitude. Therefore, competition between d(10)-PHE and the native PAHs could explain the whole attenuation of sorption to BC in unmodified sediments.