Enhanced soil washing of phenanthrene by mixed solutions of TX100 and SDBS

Increased desorption of hydrophobic organic compounds (HOCs) from soils and sediments is a key to the remediation of contaminated soils and groundwater. In this study, phenanthrene desorption from a contaminated soil by mixed solutions of a nonionic surfactant(octylphenol polyethoxylate, TX100) and an anionic surfactant (sodium dodecylbenzenesulfonate, SDBS) was investigated. Phenanthrene desorption depended on not only aqueous surfactant concentrations and phenanthrene solubility enhancement but also the soil-sorbed surfactant amount and the corresponding sorption capacity of sorbed surfactants. The added surfactant critical desorption concentrations (CDCs) for phenanthrene from soil depended on both sorbed concentrations of surfactants and their critical micelle concentrations (CMCs). Phenanthrene desorption by mixed solutions was more efficient than individual surfactants due to the low sorption loss of mixed surfactants to soil. Among the tested surfactant systems, mixed TX100 and SDBS with a 1:9 mass ratio exhibited the highest phenanthrene desorption. Mixed micelle formation, showing negative deviation of CMCs from the ones predicted by the ideal mixing theory, was primarily responsible for the significant reduction of soil-sorbed amounts of TX100 and SDBS in their mixed systems. Therefore, mixed anionic-nonionic surfactants had great potential in the area of enhanced soil and groundwater remediation.     

Influence of rhamnolipids and triton X-100 on the desorption of pesticides from soils

A rhamnolipid biosurfactant mixture produced by P. aeruginosa UG2 and the surfactant Triton X-100 were tested for their effectiveness of enhancing the desorption of trifluralin, atrazine, and coumaphos from soils. Sorption of both surfactants by the soils was significant and adequately described by the Langmuir-type isotherm. Values of maximum sorption capacity (Qmax) and Langmuir constant (Klang) did not correlate with the amount of soil organic matter. Our results indicate that clay surfaces play an important role in the sorption of surfactants. When surfactant dosages were high enough to reach soil saturation and maintain an aqueous micellar phase, pesticide desorption was only enhanced. At dosages below soil saturation, surfactants sorbed onto soil, increasing its hydrophobicity and enhancing the sorption of the pesticides by a factor of 2. Similar values of water-soil partition coefficients (Ksol*) for aged and fresh added pesticides to soils indicate that the aging process used did not significantly after the capability of either surfactant to desorb the pesticides. A model able to estimate equilibrium distributions of organic compounds in soil-aqueous-micellar systems was tested against experimental results. The determined organic carbon partition coefficients, Koc values, indicate that, on a carbon normalized basis, sorbed Rh-mix is a much better sorbent of pesticides than TX-100 or soil organic matter. These results have significant implications on determining the effectiveness of surfactants to aid soil remediation technologies.     

Geochemical modulation of pesticide sorption on smectite clay

Pesticide adsorption by soil clays can be dramatically influenced by the exchangeable cations present. Among the common exchangeable base cations in soils (Ca2+, Mg2+, K+, and Na+), K+-saturated clays frequently demonstrate the strongest affinity for pesticides. In the presence of multiple exchangeable cations in the system, we hypothesize that the magnitude of pesticide sorption to soil minerals is proportional to the fraction of clay interlayers saturated with K+ ions. To test this hypothesis, we measured sorption of three pesticides with different polarities (dichlobenil, monuron, and biphenyl) by homoionic K- and Ca-smectite (SWy-2) in KCl/CaCl2 aqueous solutions. The presence of different amounts of KCl and CaCl2 resulted in varying populations of K+ and Ca2+ on the clay exchange sites. The sorption of dichlobenil and, to a lesser extent monuron, increased with the fraction of K+ on clay mineral exchange sites. Ca- and K-SWy-2 displayed the same sorption capacities for nonpolar biphenyl. X-ray diffraction patterns indicated that at lower fractions of K+-saturation, exchangeable K+ ions were randomly distributed in clay interlayers and did not enhance pesticide sorption. At higher populations of K+ (vs Ca2+), demixing occurred causing some clay interlayers, regions, or tactoids to become fully saturated by K+, manifesting greatly enhanced pesticide sorption. The forward and reverse cation exchange reactions influenced not only K+ and Ca2+ populations on clays but also the nanostructures of clay quasicrystals in aqueous solution which plays an important, if not dominant, role in controlling the extent of pesticide sorption. Modulating the cation type and composition on clay mineral surfaces through cation exchange processes provides an environmental-safe protocol to manipulate the mobility and availability of polar pesticides, which could have applications for pesticide formulation and in environmental remediation.     

Sorption-controlled degradation kinetics of MCPA in soil

The relationship between sorption strength and degradation kinetics has been studied for the pesticide MCPA in a sandy top- and subsoil. After adding two types of sorbents (crushed peat and activated carbon) in various amounts to the sandy soils, sorption, desorption, and mineralization of 14C-MCPA were measured. The obtained Freundlich constants (KF) varied between 0.7 and 27.2 mg(1-nF) x L(nF)/kg, and the first-order mineralization rate constants varied between 0.001 and 0.128 d(-1). The results showed an inverse relationship between sorption strength and mineralization. A higher KF value corresponded to a smaller mineralization rate and less mineralization. A correlation coefficient of r2 = 0.934 between the log-transformed Freundlich desorption coefficient (K(F,des)) and the log-transformed mineralization rate constant (k) was obtained. After 7, 14, 22, and 35 days of incubation, soil samples were consecutively extracted by water, methanol, and 5 M NaOH to separate the remaining 14C into 3 different pools. The extractions showed that the mineralization only proceeded from the water extractable pool of MCPA. Thin-layer chromatography revealed a formation of small amounts of metabolites; <7% of initially added 14C was present as other compounds than 14C-MCPA in the water and methanol extractable pools. The study showed mineralization to be strongly correlated with sorption, represented by the desorption coefficient, and hence stresses the significance of bonding strength for estimating pesticide degradation in soil.     

Effect of two organic amendments on norflurazon retention and release by soils of different characteristics

The influence of two organic amendments on norflurazon sorption-desorption processes in four soils with very different physicochemical characteristics was studied in laboratory experiments to evaluate the potential leaching of this pesticide through organic fertilized soils. Sorption-desorption experiments were performed on original soils and on a mixture of these soils with urban waste compost (SUW) and a commercial amendment from olive-mill wastes (OW), at a rate of 6.25% (w/w). These mixtures were used immediately after preparation and after aging for 2 months. Norflurazon was analyzed by using a HPLC method. Norflurazon retention in original soils was related not only to the organic matter (OM) content but also to mineral surfaces present in soils. Norflurazon sorption increases largely after amendment in soils with low OM content, but the addition of exogenous OM to soils with medium OM content and/or other available adsorptive surfaces did not significantly affect norflurazon sorption. Even in some cases pesticide sorption decreases, due to the blocking of the mineral and organic soil surfaces with the amendment added. Transformation of exogenous OM during incubation depends both on the amendment added and on the type of soil and can affect sorption-desorption behavior of the soils surfaces in different manner, due to the modification of their hydrophobic-hydrophilic characteristics. Norflurazon desorption from original soils showed hysteresis in all cases, but it was not affected or even decreased in amended soils. It was a nonexpected behavior, especially in sandy soil, since it is generally assumed that a higher sorption always implies a lower mobility in soils. Norflurazon sorption must be taking place on very low affinity sites on exogenous OM through weak bindings, from which the pesticide can be easily desorbed. The application to soils of the organic amendments used in the present study could not be accepted to reduce norflurazon losses due to leaching processes.     

Variation in phenanthrene sorption coefficients with soil organic matter fractionation: the result of structure or conformation?

Sorption of phenanthrene to varying soil types was investigated to better understand sorption processes. Humic acid and humin fractions were isolated from each soil sample, and sorption coefficients were measured by batch equilibration. Samples were characterized by carbon analysis and 13C cross polarization magic angle spinning (CP/ MAS) nuclear magnetic resonance (NMR) spectroscopy. Measured organic carbon-normalized sorption coefficients (Koc) of the fractions were greater in all cases when compared to the soils. The humin fractions exhibited greater Koc values than did source samples, suggesting that fractionation may reorganize organic matter in humin resulting in an increased availability of and/or more favorable sorption domains. Mass balance calculations revealed that the sum of sorption to the fractions is greater than sorption to the whole sample. The greatest difference between sorption values was found to occur with the mineral soils, suggesting that clay minerals influence the physical conformation of soil organic matter (SOM) and availability of sorption domains. The mass balance, sorption data, and a lack of consistent trends between observed Kco values and solid-state 13C NMR data suggest that the physical conformation of SOM and chemical characteristics both play important roles in sorption processes.     

Sorption and degradation of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine in soil

The sorption/desorption and long-term fate of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) was examined using sterilized and nonsterilized soils. Two soils were used that differ mainly by the amount of total organic carbon (TOC): an agricultural topsoil (VT, 8.4% TOC) and a sandy soil (SSL, 0.33% TOC). The adsorption isotherms performed at room temperature were well-described by a linear model, which led to sorption distribution coefficients of 2.5 and 0.7 L kg(-1) for VT and SSL soils, respectively. The organic content of soil did not significantly affect HMX sorption. Over a period of 20 weeks, HMX degraded (60% disappearance) in static anaerobic nonsterile VT soil preparations. In separate experiments using UL-[14C]-HMX, 19% mineralization (liberated 14CO2) was obtained in 30 weeks. In addition, four nitroso derivatives of HMX were detected. Knowing the sorption/desorption behavior and the long-term fate of HMX in soil will help assess the effectiveness of natural attenuation for HMX removal.     

Sorption of oxytetracycline to iron oxides and iron oxide-rich soils

The sorption interactions of oxytetracycline with goethite, hematite, and two iron oxide-rich soils were investigated using batch sorption experiments. Oxytetracycline sorption coefficients for goethite and hematite increased with pH to maximum values at pH approximately 8. The sorption edge shape and desorption treatments were consistent with a surface complexation mechanism and could be described by the interaction of divalent anion species with the oxide surface. Oxytetracycline sorption to Georgeville and Orangeburg Ultisol soils decreased with pH. Chemical digestion treatments were used to deduce that soil sorption occurred by complexation to oxide coatings on clay and quartz grains. These results indicate that sorption models must consider the interaction of oxytetracycline, and other similar ionogenic compounds, with soil oxide components in addition to clays and organic matter when predicting sorption in whole soils.     

Black carbon and kerogen in soils and sediments. 2. Their roles in equilibrium sorption of less-polar organic pollutants

The first paper of this series reported that soil/sediment organic matter (SOM) can be fractionated into four fractions with a combined wet chemical procedure and that kerogen and black carbon (BC) are major SOM components in soil/sediment samples collected from the industrialized suburban areas of Guangzhou, China. The goal of this study was to determine the sorptive properties forthe four SOM fractions for organic contaminants. Sorption isotherms were measured with a batch technique using phenanthrene and naphthalene as the sorbates and four original and four Soxhlet-extracted soil/sediment samples, 15 isolated SOM fractions, and a char as the sorbents. The results showed that the sorption isotherms measured for all the sorbents were variously nonlinear. The isolated humic acid (HA) exhibited significantly nonlinear sorption, but its contribution to the overall isotherm nonlinearity and sorption capacity of the original soil was insignificant because of its low content in the tested soils and sediments. The particulate kerogen and black carbon (KB) fractions exhibited more nonlinear sorption with much higher organic carbon-normalized capacities for both sorbates. They dominate the observed overall sorption by the tested soils and sediments and are expected to be the most important soil components affecting bioavailability and ultimate fate of hydrophobic organic contaminants (HOCs). The fact that the isolated KB fractions exhibited much higher sorption capacities than when they were associated with soil/sediment matrixes suggested that a large fraction of the particulate kerogen and BC was not accessible to sorbing HOCs. Encapsulation within soil aggregates and surface coverage by inorganic and organic coatings may have caused large variations in the accessibility of fine kerogen and BC particles to HOCs and hence lowered the sorption capacity of the soil. This variability posts an ultimate challenge for precisely predicting HOC sorption by soils from the contents of different types of SOM.     

Effect of randomly methylated beta-cyclodextrin on physical properties of soils

The application of cyclodextrins in several soil remediation technologies has been increasingly studied, but little is known about their effects on soil physical properties. One of the popular soil remediation additives, randomly methylated beta-cyclodextrin (RAMEB), was found to significantly alter surface and pore properties of soil clay minerals. Therefore, in this paper we studied the effect of various RAMEB doses on physical properties of selected soils, representing a wide range of clay content (3-49%). The results showed that soil physical properties were greatly modified by RAMEB treatment. Analysis of water vapor adsorption isotherms revealed that RAMEB increased water adsorption and surface area in sandy soils and decreased them in clayey soils. An increase in adsorption energy of water in RAMEB-treated soils indicated that desorption of nonpolar pollutants can be enhanced. Water vapor desorption isotherms showed that the volumes and radii of micropores (nanometers range) increased above 1% RAMEB concentration. The micropores became more rough and complex after RAMEB treatment as deduced from an increase in fractal dimensions. The volume of soil mesopores measured by mercury intrusion porosimetry (micrometers range) gradually decreased in most soils with an increase in RAMEB concentration whereas the average mesopore radius increased, indicating that finer mesopores were blocked by RAMEB. Measurements of the granulometric composition of soils by sedimentation analysis showed that the amount of coarse-size soil fractions increased on the expense of finer fractions due to aggregation of smaller particles. Behavior of the studied soils after RAMEB treatment depended on their clay content and the dose of cyclodextrin. In clay-rich soils, strong interactions of cyclodextrins with the soil solid phase governed the resulting soil properties. In clay-poor soils, the cyclodextrin excess (not interacted with clays) played a dominant role. Modification of surface, pore, and aggregation properties of soils by RAMEB can have a significant effect in soil remediation technologies.     

Enhanced pesticide sorption by soils containing particulate matter from crop residue burns

Lack of proper techniques to isolate black carbon (BC) from soils has hindered the understanding of their roles in the sorption and environmental fate of organic contaminants in soils and sediments. The burning of crop residues may be the primary source of BC in agricultural soils. In this study, wheat (Triticum aestivum L.) and rice (Oryza sativa L.) residues were burned, and the resulting particulate matter (ashes) along with a soil were used to sorb diuron from water. Calculations indicated that the burning of crop residues may result in an appreciable level of ashes in soils. The diuron sorption isotherms on ashes were curvilinear Langmuir type, suggestive of surface adsorption and similar to that with activated carbon. Ashes were 400-2500 times more effective than soil in sorbing diuron over the concentration range of 0-6 mg/L. Sorption by wheat ash-amended soils and the degree of isotherm nonlinearity increased with increasing ash content from 0% to 1% (weight), indicating the significant contribution of wheat ash to the sorption. Calculations show that wheat ash and soil independently contributed to the sorption. Above the wheat ash content of 0.05%, the sorption was largely controlled by the ash. Density-based fractionation and repeated HCI-HF washing of wheat ash yielded carbon-enriched fractions and enhanced diuron sorption by these fractions. BC appeared primarily responsible for the high adsorptivity of ashes. Ashes arising from the burning of crop residues may be an important determinant of pesticide immobilization and environmental fate in soils.     

Clay minerals affect the stability of surfactant-facilitated carbon nanotube suspensions

Carbon nanotubes (CNTs), because of their wide application, will inevitably enter aquatic systems, but the fate and transport of their suspensions in the environment are largely unknown. Clay minerals are expected to interact with CNT suspensions, affecting their fate and bioavailability. This study investigated the influence of clay minerals (kaolinite and montmorillonite) on the stability of surfactant (SDBS, CTAB, and TX100) facilitated multiwalled CNT (MWCNT) suspensions. Adsorption of the surfactants by MWCNTs and clay minerals was also examined. This is a first study on the interaction between clay minerals and surfactant-CNT suspensions. Sorption of SDBS by clay minerals and MWCNTs followed the order MWCNTs > montmorillonite approximately kaolinite; but sorption of CTAB and TX100 followed the order montmorillonite > MWCNTs > kaolinite. For SDBS suspended MWCNTs, introduction of montmorillonite and kaolinite could not change their stability; for CTAB suspended MWCNTs, both montmorillonite and kaolinite greatly deposited the suspended MWCNTs; for TX100 suspended MWCNTs, montmorillonite could partially deposit the suspended MWCNTs, whereas kaolinite showed minimal effect. Two mechanisms of clay minerals affecting MWCNT suspensions are (1) removal of surfactants by clay minerals from solution and MWCNT surface and (2) bridging between clay mineral and MWCNTs by surfactant.     

The influence of natural organic matter rigidity on the sorption, desorption, and competitive displacement rates of 1,2-dichlorobenzene

The influence of natural organic matter (NOM) rigidity on the sorption, desorption, and competitive displacement rates of 1,2-Dichlorobenzene (1,2-DCB) was evaluated using batch reactor experiments with two surface soils (Yolo and Forbes) and a shale (Ohio). Previous characterization suggests that the shale NOM is the most reduced and condensed, the Yolo soil is the most oxidized and amorphous, and Forbes soil has an intermediate NOM structure. The rate study for each sorbent was conducted under the same reactor parameters, and 1,2-DCB mass-transfer rates were determined using the distributed first-order mass-transfer rate model based on the gamma probability density function. To measure competitive displacement rates, 1,2,4-trichlorobenzene (1,2,4-TCB) was delivered as a competitor after 34 days pre-equilibration. Higher fractions of contaminant subject to instantaneous mass transfer and much faster rates of approach to apparent sorption equilibrium are found in Yolo soil when compared with Forbes soil and the shale. The size of the instantaneously desorbing fraction thus appears inversely related to the hard carbon fraction. In the NOM compartment where mass transfer is rate-limited, rate coefficient distributions are shifted toward lower rates for desorption and competitive displacement of 1,2-DCB in Ohio shale, followed by Forbes soil. Sorption and desorption rate distributions are almost the same for the shale, while desorption rates are a few times greater than sorption rates in Yolo and Forbes soils. Mass-transfer coefficients for competitive displacement are considerably slower than those for desorption in Forbes soil and the shale. However, the mass-transfer rates for the two processes seem to be similar in Yolo soil, which has a NOM matrix comprising a relatively larger soft organic carbon fraction. The concept of "solute induced softening" is discussed as a mechanistic rationale for the experimental observations.     

Strong sorption of phenanthrene by condensed organic matter in soils and sediments

The nonhydrolyzable carbon (NHC) and black carbon (BC) in three contaminated soils and seven sediments from the Pearl River Delta and Estuary, China, were isolated upon treatments with an acid hydrolysis method and with a combustion method at 375 degrees C, respectively, and their sorption isotherms for phenanthrene (Phen) were established. It was found that NHC is chemically and structurally different from the biopolymer and humic substances and consists mainly of aliphatic and aromatic carbon using elemental analysis, 13C nuclear magnetic resonance spectroscopy (13C NMR), and Fourier transformed infrared spectroscopy (FTIR). All the sorption isotherms are nonlinear and are well fitted by the Freundlich model. The single-point organic carbon-normalized distribution coefficient (K(oc)) measured for the isolated NHC is 1.3-7.7 times higher than that for the bulk samples at the same aqueous concentration of Phen. The NHC fractions play a dominant role to the overall sorption in the bulk samples. The bulk soils and their NHC fractions have lower sorption capacity than the bulk sediments and their NHC fractions, relating to the different source of organic matter between soils and sediments. The Phen sorption capacity in the NHC samples is related significantlyto H/C ratios and aliphatic carbon, but negatively to aromatic carbon, demonstrating the important role of aliphatic carbon to the Phen sorption and the fate in the investigated soils and sediments.     

Distribution of aged 14C-PCB and 14C-PAH residues in particle-size and humic fractions of an agricultural soil

Organic matter is considered to be the single most importantfactor limiting availability and mobility of persistent organic pollutants (POPs) in soil. This study aimed to characterize the distribution of 14C-PCB (congeners 28 and 52) and 14C-PAH (fluoranthene and benzo[a]pyrene) residues in an Orthic Luvisol soil obtained from two lysimeter studies initiated in 1990 at the Agrosphere Institute (Forschungszentrum Jülich GmbH, Germany). The lysimeter soils contained a low-density OM fraction, isolated during soil washing, which contained a significant fraction (3-12%) of the total 14C-activity. Soils were also fractionated according to three particle sizes: >20, 20-2, and <2 microm. Relative affinity values of 14C-activity for the different particle sizes varied in the order 20-2 microm > (<2 microm) approximately (>20 microm) for the PCBs. Relative affinity values of 14C-activity for the different particle sizes varied in the order 20-2 microm > (<2 microm) > (>20 microm) for the PAHs. The distribution of 14C-PCB or 14C-PAH residues in the organic and inorganic matrixes of the particle-size fractions was determined using methyl isobutyl ketone (MIBK). 14C-PCB and 14C-PAH-associated activities were primarily located in the humin fraction of the 20-2 and <2 microm particle-size fractions of the soil. A small fraction was associated with the fulvic and humic acid fractions; these were quantitatively more important for the PAHs than the PCBs. There appeared to be a high degree of association of 14C-activity with the mineral fraction following MIBK separation of the humic fractions, ranging between 8 and 52% for 14C-PCBs and 57-80% for 14C-PAHs. The mineral (inorganic) component of the soils apparently played a significant (previously unreported) role in the sequestration of both PCBs 28 and 52 and the PAHs fluoranthene and benzo[a]pyrene.     

Time-dependent changes of zinc speciation in four soils contaminated with zincite or sphalerite

The long-term speciation of Zn in contaminated soils is strongly influenced by soil pH, clay, and organic matter content as well as Zn loading. In addition, the type of Zn-bearing contaminant entering the soil may influence the subsequent formation of pedogenic Zn species, but systematic studies on such effects are currently lacking. We therefore conducted a soil incubation study in which four soils, ranging from strongly acidic to calcareous, were spiked with 2000 mg/kg Zn using either ZnO (zincite) or ZnS (sphalerite) as the contamination source. The soils were incubated under aerated conditions in moist state for up to four years. The extractability and speciation of Zn were assessed after one, two, and four years using extractions with 0.01 M CaCl(2) and Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy, respectively. After four years, more than 90% of the added ZnO were dissolved in all soils, with the fastest dissolution occurring in the acidic soils. Contamination with ZnO favored the formation of Zn-bearing layered double hydroxides (LDH), even in acidic soils, and to a lesser degree Zn-phyllosilicates and adsorbed Zn species. This was explained by locally elevated pH and high Zn concentrations around dissolving ZnO particles. Except for the calcareous soil, ZnS dissolved more slowly than ZnO, reaching only 26 to 75% of the added ZnS after four years. ZnS dissolved more slowly in the two acidic soils than in the near-neutral and the calcareous soil. Also, the resulting Zn speciation was markedly different between these two pairs of soils: Whereas Zn bound to hydroxy-interlayered clay minerals (HIM) and octahedrally coordinated Zn sorption complexes prevailed in the two acidic soils, Zn speciation in the neutral and the calcareous soil was dominated by Zn-LDH and tetrahedrally coordinated inner-sphere Zn complexes. Our results show that the type of Zn-bearing contaminant phase can have a significant influence on the formation of pedogenic Zn species in soils. Important factors include the rate of Zn release from the contaminant phases and effects of the contaminant phase on bulk soil properties and on local chemical conditions around weathering contaminant particles.     

Sorption of phenanthrene by nonhydrolyzable organic matter from different size sediments

Nonhydrolyzable organic carbon (NHC) and sorption isotherms of phenanthrene (Phen) on six size-fractionated NHC fractions in two sediments from the Pearl River and Estuary, South China, were investigated. It was found that NHC including ancient organic carbon, black carbon, resistant aquatic organic carbon, and aged soil organic carbon consists mainly of aliphatic and aromatic carbon using 13C nuclear magnetic resonance spectroscopy. The sorption isotherms of Phen by the size-fractionated NHC fractions are nonlinear and are well-fitted to the Freundlich model. For the estuary sediment, the NHC contents and the organic carbon-normalized distribution coefficients (Koc) in the size fractions increase with decreasing particle size. The clay NHC fraction contributes to 70% of the Phen sorption by the bulk NHC isolate. However, for the contaminated river sediment, the NHC contents and the Koc values exhibit no regular variations among the size fractions. The Phen sorption capacities on the size-fractionated NHC fractions of the two sediments are significantly related to their H/C ratios and aliphatic carbon, but negatively to aromatic carbon. The fine-particle NHC fractions with high aliphatic carbon and H/C ratio play a very important role in the sorption, transport, and fate of Phen by the investigated sediments.     

Multiscale assessment of methylarsenic reactivity in soil. 1. Sorption and desorption on soils

Methylated forms of arsenic (As), monomethylarsenate (MMA), and dimethylarsenate (DMA) have historically been used as herbicides and pesticides. Because of their large application to agriculture fields and the toxicity of MMA and DMA, the persistency of these compounds in the environment is of great concern. MMA and DMA sorption and desorption were investigated in soils, varying in mineralogical and organic matter (OM) contents. Sorption studies showed that the MMA sorption capacity and rate were greater than DMA sorption. Al/Fe-oxyhydroxides were the main sorbents in the soils, and the sorption capacity was proportional to the Al/Fe concentration in the soils. Extended X-ray absorption fine structure (EXAFS) studies showed that both MMA/DMA-Fe interatomic distances were around 3.3 ?, which were indicative of bidentate binuclear inner-sphere complex formation. Desorption studies showed that not all of the sorbed MMA or DMA was desorbed due to the strong binding between MMA/DMA and Al/Fe-oxyhydroxide surfaces via possible inner-sphere complex formation. The amount of the desorbed MMA and DMA decreased as the sorption residence time increased. For example, 77% of sorbed MMA was desorbed from the Reybold subsoil after 1 day residence time, while 66% of sorbed MMA was desorbed from the soil after six months of residence time. The decreases in desorption were likely due to As speciation changes from MMA/DMA to inorganic arsenate, which was more strongly bound to the surface.     

Pesticide sorption and desorption by lignin described by an intraparticle diffusion model

Lignin was used as a model compound for soil organic matter to gain insight into the mechanisms that control the kinetics of pesticide sorption and desorption. Hydrolytic lignin was immobilized in a matrix of alginate gel, and sorption-desorption experiments were undertaken with isoproturon. Sorption increased with time and was close to equilibrium after 14 days. Desorption was measured after sorption for different time intervals and for a number of successive desorption steps of different lengths. The results showed strong differences between the sorption and desorption isotherms. The ratio of sorbed to dissolved pesticide approached and even exceeded the equilibrium ratio, depending on the number of desorption steps and the length of each equilibration period. A numerical diffusion model was developed to describe radial diffusion into the lignin particles in combination with Freundlich sorption inside the particles. Key model parameters were adjusted to fit the sorption data, and the same parameters were then used to predict stepwise desorption. Desorption was well described by the model, which suggests that sorption and desorption were driven by the same mechanism and occurred at the same rate. The observed difference between the sorption and desorption isotherms could be fully explained by the nonattainment of equilibrium due to slow diffusion into and out of the lignin particles.     

Particle-scale understanding of the bioavailability of PAHs in sediment

This study reports results of sediment bioslurry treatment and earthworm bioaccumulation for polycyclic aromatic hydrocarbon (PAH) contaminants found in sediment dredged from Milwaukee Harbor. A significant finding was that bioslurry treatment reduced PAHs on the sediment clay/silt fraction but not on the sediment coal-derived fraction and that PAH reduction in the clay/silt fraction correlated with substantial reduction in earthworm PAH bioaccumulation. These findings are used to infer PAH bioavailability from characterization of particle-scale PAH distribution, association, and binding among the principal particle fractions in the sediment. The results are consistent with work showing that the sediment comprised two principal particle classes for PAHs, coal-derived and clay/silt, each having much different PAH levels, release rates, and desorption activation energies. PAH sorption on coal-derived particles is associated with minimal biodegradation, slow release rates, and high desorption activation energies, while PAH sorption on clay/silt particles is associated with significant potential biodegradability, relatively fast release rates, and lower desorption activation energies. These characteristics are attributed to fundamental differences in the organic matter to which the PAHs are sorbed. Although the majority of the PAHs are found preferentially on coal-derived particles, the PAHs on the clay/silt sediment fraction are more mobile and available, and thus potentially of greater concern. This study demonstrates that a suite of tests comprising both bioassays and particle-scale investigations provide a basis to assess larger-scale phenomena of biotreatment of PAH-impacted sediments and bioavailability and potential toxicity of PAH contaminants in sediments. Improved understanding of contaminant bioavailability aids decision-making on the effectiveness of biotreatment of PAH-impacted sediments and the likelihood for possible reuse of dredged sediments as reclaimed soil or fill.