Enhanced Desorption of Phenanthrene from Soils Using Hydroxypropyl‐β‐cyclodextrin: Experimental Results and Model Predictions

Objective of this study was to evaluate the effects of hydroxypropyl‐β‐cyclodextrin (HPCD) on the removal of phenanthrene from solid phase. Batch tests for the phenanthrene distribution between aqueous and solid phase were conducted in the presence of HPCD. Column tests and numerical simulations were conducted to evaluate the roles of HPCD cavities and interaction rates between water, HPCD, and solid phase in the enhanced removal of phenanthrene. Experimental results showed that HPCD was effective in removing sorbed phenanthrene from subsurface environment, primarily due to its negligible sorption to the solid phase and the partitioning of phenanthrene into HPCD cavities. From the numerical simulations, it was found that rate‐limited partitioning of phenanthrene into HPCD cavities was most influential factor in the enhanced elution of phenanthrene. Sorption and desorption rate of phenanthrene between aqueous and solid phase was very fast or near equilibrium state. Interaction rates of contaminant between water, HPCD, and solid phase could be affected by other factors such as soil types and organic matter contents. Results from this study implied that HPCD flushing could be effectively applied for the removal of hydrophobic organic pollutants existing in the soils as sorbed or NAPL state.     

Simultaneous removal of organic compounds and heavy metals from soils by electrokinetic remediation with a modified cyclodextrin

Thousands of sites are contaminated with both heavy metals and organic compounds and these sites pose a major threat to public health and the environment. Previous studies have shown that electrokinetic remediation has potential to remove heavy metals and organic compounds when they exist individually in low permeability soils. This paper presents the feasibility of using cyclodextrins in electrokinetic remediation for the simultaneous removal of heavy metals and polycyclic aromatic hydrocarbons (PAHs) from low permeability soils. Kaolin was selected as a model low permeability soil and it was spiked with phenanthrene as well as nickel at concentrations of 500 mg kg-1 each to simulate typical mixed field contamination. Bench-scale electrokinetic experiments were conducted using hydroxypropyl beta-cyclodextrin (HPCD) at low (1%) and high (10%) concentrations and using deionized water in control test. A periodic voltage gradient of 2VDC cm-1 (with 5 d on and 2 d off) was applied to all the tests, and 0.01 M NaOH was added during the experiments to maintain neutral pH conditions at anode. In all tests, nickel migrated as Ni2+ ions towards the cathode and most of it was precipitated as Ni(OH)2 within the soil close to the cathode due to high pH condition generated by electrolysis reaction. The solubility of phenanthrene in the flushing solution and the amount of electroosmotic flow controlled the migration and removal of phenanthrene in all the tests. Even though high flow was generated in tests using deionized water and 1% HPCD, migration and removal of phenanthrene was low due to low solubility of phenanthrene in these solutions. The test with 10% HPCD solution showed higher solubility of phenanthrene which caused it migrate towards the cathode, but further migration and removal was retarded due to reduced electric current and electroosmotic flow. Approximately one pore volume of flushing resulted in approximately 50% removal of phenanthrene from the soil near the anode. Sustained higher electroosmotic flow with higher concentration cyclodextrin and maintaining low soil pH near cathode should be investigated to increase removal efficiency of both phenanthrene and nickel.     

The partitioning of alkylphenolic surfactants and polybrominated diphenyl ether flame retardants in activated sludge batch tests

Polybrominated diphenyl ethers and nonylphenol polyethoxylates have been reported to be estrogenic and may enter the aquatic environment through the discharge of treated sewage effluent. Therefore, their fate during wastewater treatment processes is an important factor in determining their environmental impact. Batch tests with activated sludge from a Husmann apparatus were used to determine the effects of physico-chemical properties and sludge characteristics on the partitioning of polybrominated diphenyl ether flame retardants and nonylphenol polyethoxylate surfactants during biological wastewater treatment. Hydrophobic compounds, those with high logK(ow) values, were sorbed more rapidly and to a greater extent to the solid phase than more soluble compounds. For these hydrophobic compounds sorption may become an increasingly important removal mechanism as sludge age and therefore solids content increase. The initial rate of partitioning was greatest for the most hydrophobic compounds but all rates diminished with time as a result of progressive saturation of sorbent binding sites, a reduction of sorbate availability and as a consequence of the system reaching equilibrium. The sorption of polybrominated diphenyl ethers fit Freundlich adsorption isotherms demonstrating generally increasing adsorption capacity and efficiency with increasing hydrophobic nature. A correlation between increasing logK(ow) and increasing organic matter content was also observed for both polybrominated diphenyl ethers and nonylphenol polyethoxylates indicating the organic content of mixed liquor will also be influential in removing compounds during wastewater treatment.     

Linking desorption kinetics to phenanthrene biodegradation in soil

The desorption of polycyclic aromatic hydrocarbons (PAHs) often exhibits a biphasic profile similar to that observed for biodegradation whereby an initial rapid phase of degradation or desorption is followed by a phase of much slower transformation or release. Most investigations to-date have utilised a polymeric sorbent, such as Tenax, to characterise desorption, which is methodologically unsuitable for the analysis of soil. In this study, desorption kinetics of ¹⁴C-phenanthrene were measured by consecutive extraction using aqueous solutions of hydroxypropyl-β-cyclodextrin (HPCD). The data indicate that the fraction extracted after 24 h generally approximated the linearly sorbed, rapidly desorbing fraction (F_rap), calculated using a three-compartment model. A good linear correlation between phenanthrene mineralised and F_rap was observed (r² = 0.89; gradient = 0.85; intercept = 8.20). Hence HPCD extraction (24 h) and first-order three-compartment modelling appear to provide an operationally straightforward tool for estimating mass-transfer limited biodegradation in soil.     

The estimation of PAH bioavailability in contaminated sediments using hydroxypropyl-beta-cyclodextrin and Triton X-100 extraction techniques

A study was conducted to investigate whether cyclodextrins and surfactants can be used to predict polycyclic aromatic hydrocarbon (PAH) bioavailability in contaminated sediments. Two sediment samples were extracted with aqueous solutions of hydroxypropyl-beta-cyclodextrin (HPCD) and Triton X-100. PAH removal during extraction was compared with PAH removal during biodegradation and solid-phase extraction. The latter two methods were used as reference methods to establish which part of the PAHs could be biodegraded and to what extent biodegradation was governed by bioavailability limitations. It was demonstrated that HPCD extraction followed solid-phase extraction and removed primarily readily bioavailable PAHs, while Triton X-100 extracted both readily and poorly bioavailable PAHs. Moreover, HPCD did not affect the degradation of PAHs in biodegradation experiments, while Triton X-100 enhanced the degradation of low molecular weight PAHs. It was concluded that HPCD extraction may provide a good method for the prediction of PAH bioavailability. Triton X-100 extraction is unfit for the prediction of PAH bioavailability.     

Fugacity modelling to predict the distribution of organic contaminants in the soil:oil matrix of constructed biopiles

Level I and II fugacity approaches were used to model the environmental distribution of benzene, anthracene, phenanthrene, 1-methylphenanthrene and benzo[a]pyrene in a four phase biopile system, accounting for air, water, mineral soil and non-aqueous phase liquid (oil) phase. The non-aqueous phase liquid (NAPL) and soil phases were the dominant partition media for the contaminants in each biopile and the contaminants differed markedly in their individual fugacities. Comparison of three soils with different percentage of organic carbon (% org C) showed that the % org C influenced contaminant partitioning behaviour. While benzene showed an aqueous concentration worthy of note for leachate control during biopiling, other organic chemicals showed that insignificant amount of chemicals leached into the water, greatly reducing the potential extent of groundwater contamination. Level II fugacity model showed that degradation was the dominant removal process except for benzene. In all three biopile systems, the rate of degradation of benzo(a)pyrene was low, requiring more than 12 years for soil concentrations from a spill of about 25 kg (100 mol) to be reduced to a concentration of 0.001 microgg(-1). The removal time of 1-methylphenanthrene and either anthracene or phenanthrene was about 1 and 3 years, respectively. In contrast, benzene showed the highest degradation rate and was removed after 136 days in all biopile systems. Overall, this study confirms the association of risk critical contaminants with the residual saturation in treated soils and reinforces the importance of accounting for the partitioning behaviour of both NAPL and soil phases during the risk assessment of oil-contaminated sites.     

Comparison of selected non-exhaustive extraction techniques to assess PAH availability in dissimilar soils

Recently, it has become apparent that the use of total contaminant concentrations as a measure of potential contaminant exposure to plants or soil organisms is inappropriate and that bioavailability of contaminants is a better measure of potential exposure. In light of this, non-exhaustive extraction techniques are being investigated to assess their appropriateness in determining bioavailability. In this study, phenanthrene extractability using hydroxypropyl-beta-cyclodextrin (HPCD) and desorption kinetics using butan-1-ol (BuOH) were determined in three dissimilar spiked soils. The soils were extracted after 1 d, 40 d and 80 d of soil-compound contact time. The amount of phenanthrene extracted by HPCD was compared to the rapidly desorbed fraction removed by BuOH. Further experiments using the same soils and extraction methods to assess the relative extractability of phenanthrene, pyrene and benzo(a)pyrene were conducted. Overall, the extraction methods used in this study had different extraction efficiencies. Results suggest that as compound hydrophobicity increased, BuOH became a more exhaustive extractant with respect to HPCD, especially for soils with high clay and organic matter content. These results are important as they highlight differences between two contrasting non-exhaustive extraction techniques both of which have been suggested to be appropriate in the assessment of bioavailability.     

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.     

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.     

Effects of compositional heterogeneity and nanoporosity of raw and treated biomass-generated soot on adsorption and absorption of organic contaminants

A biomass-generated soot was sequentially treated by HCl-HF solution, organic solvent, and oxidative acid to remove ash, extractable native organic matter (EOM), and amorphous carbon. The compositional heterogeneity and nano-structure of the untreated and treated soot samples were characterized by elemental analysis, thermal gravimetric analysis, BET-N₂ surface area, and electron microscopic analysis. Sorption properties of polar and nonpolar organic pollutants onto the soot samples were compared, and individual contributions of adsorption and absorption were quantified. The sorption isotherms for raw sample were practically linear, while were nonlinear for the pretreated-soot. The removal of EOM enhanced adsorption and reduced absorption, indicating that EOM served as a partitioning phase and simultaneously masked the adsorptive sites. By drastic-oxidation, the outer amorphous carbon and the inner disordered core of the soot particles were completely removed, and a fullerene-like nanoporous structure (aromatic shell) was created, which promoted additional π-π interaction between phenanthrene and the soot.     

Distribution of polycyclic aromatic hydrocarbons in soil-water system containing a nonionic surfactant

The effect of a nonionic surfactant, Triton X-100 (TX100), on the distribution of four representative polycyclic aromatic hydrocarbons (PAHs), phenanthrene, fluorene, acenaphthene and naphthalene, in soil-water system was studied on a natural soil. The apparent soil-water distribution coefficient with surfactant (Kd*) for these compounds increased when TX100 equilibrium concentration from zero to around the critical micelle concentration (CMC), followed by a decrease in Kd* at TX100 equilibrium concentration greater than CMC. This is a direct result of surfactant sorption onto soil followed by PAHs partitioning to the sorbed surfactant. The values of carbon-normalized solute distribution coefficient (Kss) with the sorbed TX100 are greater than the corresponding partition coefficients with soil organic matter (Koc), which indicates the soil-sorbed nonionic surfactant is more effective per unit mass as a partitioning medium than the native soil organic matter for PAHs. When Kd* = Kd the corresponding initial concentration of surfactant was defined as critical washing concentration (CWC). Depending on the surfactant initial concentration below or above the CWC, the addition of nonionic surfactant can enhance the retardation of soil for PAHs or promote the removal of PAHs from soil, respectively. The values of Kd* and CWC can be predicted by a model, which correlates them with the compounds' octanol-water partition coefficients (Kow), soil property and the amount of soil-sorbed surfactant.     

Towards a more appropriate water based extraction for the assessment of organic contaminant availability

This study correlated extractabilities of 37 d aged phenanthrene residues in four dissimilar soils with the fraction that was available for earthworm (Lumbricus rubellus) accumulation and microorganism (Pseudomonas sp.) mineralisation. Extractability was determined using two established techniques, namely, (1) a water based extraction using CO(2) equilibrated water and (2) an aqueous based hydroxypropyl-beta-cyclodextrin (HPCD) extraction. Results showed no relationship between earthworm accumulation and phenanthrene extractability using either HPCD (r(2)=0.07; slope=-4.76; n=5) or the water based extraction (r(2)=0.31; slope=-5.34; n=5). Earthworm accumulation was overestimated by both techniques. In contrast, the fraction of phenanthrene extractable using both the HPCD technique and the water based extraction correlated strongly with microbial mineralisation. However, the slopes of these linear relationships were 0.48 (r(2)=0.96; n=10), and 0.99 (r(2)=0.88; n=10) for the water based extraction and HPCD, respectively. Thus, the HPCD extraction provided values that were numerically close to the mineralisation values, whilst the water based extraction values were approximately half the mineralisation values. It is submitted that HPCD extraction provided an appropriate method of assessing the fraction of contaminant available for microbial mineralisation in these dissimilar soils.     

Hydroxypropyl-β-cyclodextrin extractability and bioavailability of phenanthrene in humin and humic acid fractions from different soils and sediments

Organic matter (OM) plays a vital role in controlling polycyclic aromatic hydrocarbon (PAH) bioavailability in soils and sediments. In this study, both a hydroxypropyl-β-cyclodextrin (HPCD) extraction test and a biodegradation test were performed to evaluate the bioavailability of phenanthrene in seven different bulk soil/sediment samples and two OM components (humin fractions and humic acid (HA) fractions) separated from these soils/sediments. Results showed that both the extent of HPCD-extractable phenanthrene and the extent of biodegradable phenanthrene in humin fraction were lower than those in the respective HA fraction and source soil/sediment, demonstrating the limited bioavailability of phenanthrene in the humin fraction. For the source soils/sediments and the humin fractions, significant inverse relationships were observed between the sorption capacities for phenanthrene and the amounts of HPCD-extractable or biodegradable phenanthrene (p?<?0.05), suggesting the importance of the sorption capacity in affecting desorption and biodegradation of phenanthrene. Strong linear relationships were observed between the amount of HPCD-extractable phenanthrene and the amount degraded in both the bulk soils/sediments and the humin fractions, with both slopes close to 1. On the other hand, in the case of phenanthrene contained in HA, a poor relationship was observed between the amount of phenanthrene extracted by HPCD and the amount degraded, with the former being much less than the latter. The results revealed the importance of humin fraction in affecting the bioavailability of phenanthrene in the bulk soils/sediments, which would deepen our understanding of the organic matter fractions in affecting desorption and biodegradation of organic pollutants and provide theoretical support for remediation and risk assessment of contaminated soils and sediments.     

Influence of surfactant sorption on the removal of phenanthrene from contaminated soils

Laboratory column flushing experiments were conducted to remove phenanthrene from contaminated soils by Triton X-100 (TX100) with an aim to investigating the effect of surfactant sorption on the performance of surfactant-enhanced remediation process. The effluent concentration of phenanthrene from soil columns showed strong dependence on the sorption breakthrough curves of TX100. The removal of phenanthrene from contaminated soils was enhanced only when the sorption breakthrough of TX100 occurred and the influent concentration of TX100 was greater than the critical enhanced flushing concentration (CEFC). The sorption of surfactant onto soils and the subsequent partitioning of contaminants into soil-sorbed surfactant had a significant effect on the solute equilibrium distribution coefficient (KD) and thus the flushing efficiency for phenanthrene. A model was developed to predict KD and CEFC values for simulating the performance of surfactant-enhanced flushing for contaminated soils. These results are of practical interest in developing effective and safe surfactant-enhanced remediation technologies.     

Effects of lipids on the sorption of hydrophobic organic compounds on geosorbents: a case study using phenanthrene

The impact of the lipid fraction of natural geosorbents on the sorption of a polycyclic aromatic hydrocarbon was assessed using several experiments. In the first set of experiments phenanthrene was sorbed on a coastal sediment as well as on its humin and humic acid fractions before and after lipid extraction. Before lipid extraction, sorption shows dominantly partitioning characteristics. However, the extraction of lipids from sediment and humin drastically increases, by up to one order of magnitude, their sorption affinity for phenanthrene at low sorbate concentrations, resulting in increased isotherm nonlinearity. This effect is less pronounced for humic acids. One mechanism proposed for the increasing sorption is that lipids, despite their very low relative abundance in the sediments, can compete with phenanthrene for specific high affinity sorption sites (e.g., matrix pores and adsorption sites). This competition is not surprising considering the similar hydrophobic nature of lipids and phenanthrene. Lipids, or any non-polar molecules, could also act like plasticizers by swelling rigid domains and disrupting high affinity sites. In both cases, the removal of lipids (and extraction solvents) makes those sites available for phenanthrene. These provide alternative explanations to the previously proposed “solvent conditioning effect” believed to occur when geosorbents are treated with non-polar solvents modifying the matrix structure, an effect yet to be proven at molecular scale. To further investigate the impact of lipids on sorption, other independent experiments were performed. In a second experiment, re-addition of lipids to the extracted sediment restored the sorption isotherm linearity observed in the native material supporting the absence of irreversible extraction artifacts. However, high addition of lipids (i.e., after saturation of high affinity sites) seems to also enlarge the low affinity partitioning domain. These results are consistent with dual-mode, hole-filling, sorption models involving diffusion. In the final set of experiments, solid-state ¹⁹F-NMR using F-labeled lipids sorbed onto the sediments confirmed that lipids may be in different domains (mobile or rigid) that interact or not with phenanthrene. The possible effects of lipid removal on sorption have been overlooked and should be considered when geosorbents are pretreated.     

Interaction of bisphenol A with dissolved organic matter in extractive and adsorptive removal processes

The fate of endocrine disrupting chemicals (EDCs) in natural and engineered systems is complicated due to their interactions with various water constituents. This study investigated the interaction of bisphenol A (BPA) with dissolved organic matter (DOM) and colloids present in surface water and secondary effluent as well as its adsorptive removal by powdered activated carbons. The solid phase micro-extraction (SPME) method followed by thermal desorption and gas chromatography-mass spectrometry (GC-MS) was utilized for determining the distribution of BPA molecules in water. The BPA removal by SPME decreased with the increased DOM content, where the formation of BPA-DOM complexes in an aqueous matrix was responsible for the reduced extraction of BPA. Colloidal particles in water samples sorbed BPA leading to the marked reduction of liquid phase BPA. BPA-DOM complexes had a negative impact on the adsorptive removal of BPA by powered activated carbons. The complex formation was characterized based on Fourier transform infrared (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy, along with the calculation of molecular interactions between BPA and functional groups in DOM. It was found that the hydrogen bonding between DOM and BPA would be preferred over aromatic interactions. A pseudo-equilibrium molecular coordination model for the complexation between a BPA molecule and a hydroxyl group of the DOM was developed, which enabled estimation of the maximum sorption site and complex formation constant as well as prediction of organic complexes at various DOM levels.     

均匀电场下多环芳烃在土壤中的迁移

当循环电解液流速为800 mL/h,电解液为无菌水时,电渗流流量、菲和芘在土壤中迁移量在电压梯度为1 V/cm作用下比电压梯度为0.5 V/cm时要多;电动注入表面活性剂Tween80和HPCD均可以提高菲和芘在土壤中的迁移,注入Tween80和HPCD浓度分别为500和1 000 mg/L时,相应地Phe提高5.8倍和11.7倍、芘提高2倍和3.4倍;而BaP在水中的溶解度太小,电场作用和电动注入表面活性剂对BaP在土壤中的迁移量影响很小。为建立电动修复有机污染物污染提供了技术基础。     

In situ iron activated persulfate oxidative fluid sparging treatment of TCE contamination--a proof of concept study

In situ chemical oxidation (ISCO) is considered a reliable technology to treat groundwater contaminated with high concentrations of organic contaminants. An ISCO oxidant, persulfate anion (S(2)O(8)(2-)) can be activated by ferrous ion (Fe(2+)) to generate sulfate radicals (E(o)=2.6 V), which are capable of destroying trichloroethylene (TCE). The property of polarity inhibits S(2)O(8)(2-) or sulfate radical (SO(4)(-)) from effectively oxidizing separate phase TCE, a dense non-aqueous phase liquid (DNAPL). Thus the oxidation primarily takes place in the aqueous phase where TCE is dissolved. A bench column study was conducted to demonstrate a conceptual remediation method by flushing either S(2)O(8)(2-) or Fe(2+) through a soil column, where the TCE DNAPL was present, and passing the dissolved mixture through either a Fe(2+) or S(2)O(8)(2-) fluid sparging curtain. Also, the effect of a solubility enhancing chemical, hydroxypropyl-beta-cyclodextrin (HPCD), was tested to evaluate its ability to increase the aqueous TCE concentration. Both flushing arrangements may result in similar TCE degradation efficiencies of 35% to 42% estimated by the ratio of TCE degraded/(TCE degraded+TCE remained in effluent) and degradation byproduct chloride generation rates of 4.9 to 7.6 mg Cl(-) per soil column pore volume. The addition of HPCD did greatly increase the aqueous TCE concentration. However, the TCE degradation efficiency decreased because the TCE degradation was a lower percentage of the relatively greater amount of dissolved TCE by HPCD. This conceptual treatment may serve as a reference for potential on-site application.     

Indoor/outdoor connections exemplified by processes that depend on an organic compound's saturation vapor pressure

Outdoor and indoor environments are profitably viewed as parts of a whole connected through various physical and chemical interactions. This paper examines four phenomena that share a dependence on vapor pressure—the extent to which an organic compound in the gas phase sorbs on airborne particles, sorbs on surfaces, sorbs on particles collected on a filter or activates trigeminal nerve receptors. It also defines a new equilibrium coefficient for the partitioning of organic compounds between an airstream and particles collected by a filter in that airstream. Gas/particle partitioning has been studied extensively outdoors, but sparingly indoors. Gas/surface partitioning occurs primarily indoors while gas/filter partitioning occurs at the interface between outdoors and indoors. Activation of trigeminal nerve receptors occurs at the human interface. The logarithm of an organic compound's saturation vapor pressure correlates in a linear fashion with the logarithms of equilibrium coefficients characteristic of each of these four phenomena. Since, to a rough approximation, the log of an organic compound's vapor pressure scales with its molecular weight, molecular weight can be used to make first estimates of the above processes. For typical indoor conditions, only larger compounds with lower-saturation vapor pressures (e.g., tetracosane, pentacosane, or di-2-ethylhexyl phthalate) have airborne particle concentrations comparable to or larger than gas phase concentrations. Regardless of a compound's vapor pressure, the total mass sorbed on indoor airborne particles is quite small compared to the total sorbed on indoor surfaces, reflecting the large difference in surface areas between particles within a room and surfaces within a room. If the actual surface areas are considered, accounting for roughness and porosity, the surface concentration of organics sorbed on typical airborne particles appears to be comparable to the surface concentration of organics sorbed on indoor carpets, walls and other materials (based on data from several studies in the literature). Mirroring the importance of phase distributions outdoors, an organic compound's indoor lifetime, fate and even health impacts depend on its distribution between phases and among surfaces.     

A predictive model for copper partitioning to suspended particulate matter in river waters

A chemical equilibrium-based predictive model expressing Cu partitioning as a function of aqueous and solid phase characteristics was developed. The model takes into account only the most important factors that govern Cu partitioning, and therefore results in a relatively simple formulation. It assumes particulate organic carbon (POC) and dissolved organic carbon (DOC) binding sites play the most important role in solid and aqueous phases. The model formulation assumed one-surface site and two dissolved organic matter (DOM) sites, and included the "solids effect". Proton effects were considered for both the particle surface sites and the DOM. The model was calibrated with data for samples collected from the Susquehanna River, and validated with White Clay Creek and Delaware River samples. Copper partitioning in natural water systems with different pH, and concentrations of alkalinity, DOC, POC, total suspended solids (TSS), and total copper was predicted reasonably well.