Sorption of atrazine and phenanthrene by organic matter fractions in soil and sediment

Atrazine and phenanthrene (Phen) sorption by nonhydrolyzable carbon (NHC), black carbon (BC), humic acid (HA) and whole sediment and soil samples was examined. Atrazine sorption isotherms were nearly linear. The single-point organic carbon (OC)-normalized distribution coefficients (K_OC) of atrazine for the isolated HA1, NHC1 and BC1 from sediment 1 (ST1) were 36, 550, and 1470 times greater than that of ST1, respectively, indicating the importance of sediment organic matter, particularly the condensed fractions (NHC and BC). Similar sorption capacity of atrazine and Phen by NHC but different isotherm nonlinearity indicated different sorption domains due to their different structure and hydrophobicity. The positive relationship between (O + N)/C ratios of NHC and atrazine log K_OC at low concentration suggests H-bonding interactions. This study shows that sediment is probably a less effective sorbent for atrazine than Phen, implying that atrazine applied in sediments or soils may be likely to leach into groundwater.     

Responses of kinetics and capacity of phenanthrene sorption on sediments to soil organic matter releasing

Soil organic matter (SOM) releasing with dissolved organic matter (DOM) formed in solution was confirmed in a sediment/water system, and the effects of SOM releasing on the sorption of phenanthrene on sediments were investigated. Inorganic salt (0–0.1 mol L^?1 NaCl) was used to adjust SOM releasing, and two sediments were prepared, the raw sediment (S1) from Weihe River, Shann’xi, China, and the eluted sediments with and without DOM supernatant remained, termed as S2a and S2b, respectively. The FTIR and ¹H NMR analysis indicate that the low molecular weight hydrophilic SOM fraction released prior to the high molecular weight hydrophobic fraction. As a response, phenanthrene sorption kinetics on S1 showed atypical and expressed as three stages: rapid sorption, pseudo sorption with partial desorption, and slow sorption, thus a defined “sorption valley” occurred in kinetic curve. In all cases, partition dominates the sorption, and sorption capacity (K_d) ranked as S2b > S1 > S2a. Compared with the alterations of sediment characters, DOM solubilization produced by SOM releasing exhibited a greater inhibitory effect on sorption with a relative contribution of 0.67. Distribution coefficients (K_doc) of PHE into DOM clusters were 2.10?×?10⁴–4.18?×?10⁴ L kg^?1, however a threshold concentration of 6.83 mg L^?1 existed in DOM solubilization. The study results will help to clarify PAHs transport and their biological fate in a sediment/water system.     

Relation between PAH and black carbon contents in size fractions of Norwegian harbor sediments

Distributions of total organic carbon (TOC), black carbon (BC), and polycyclic aromatic hydrocarbons (PAH) were investigated in different particle size fractions for four Norwegian harbor sediments. The total PAH (16-EPA) concentrations ranged from 2 to 113 mg/kg dry weight with the greatest fraction of PAH mass in the sand fraction for three of the four sediments. TOC contents ranged from 0.84% to 14.2% and BC contents from 0.085% to 1.7%. This corresponds to organic carbon (OC = TOC - BC) contents in the range of 0.81-14% and BC:TOC ratios of 1.3-18.1%. PAH isomer ratios suggested that the PAH in all four sediments were of pyrogenic origin. Furthermore, stronger correlations between PAH versus BC (r2 = 0.85) than versus OC (r2 = 0.15) were found. For all size fractions and bulk sediments, the PAH-to-BC ratios for the total PAHs were on average 6+/-3 mg PAH/g BC. These results suggest that PAH distributions were dominated by the presence of BC, rather than OC. As sorption to BC is much stronger than sorption to OC, this may result in significantly lower dissolved concentrations of PAH than expected on the basis of organic carbon partitioning alone.     

Persistence,variance and toxic levels of organochlorine pesticides in fluvial sediments and the role of black carbon in their retention

The present study assesses the persistence and variation of organochlorine pesticides (OCPs) and their regulation by total organic carbon (TOC) and black carbon (BC) in freshwater sediment. Sediment samples from the Yamuna River, a major tributary of the Ganges (one of the most populated and intensively used rivers in Asia), had high levels of Σ₂₀OCPs (21.41 to 139.95 ng g^?1). β-Hexachlorocyclohexane (β-HCH) was the most predominant component. ΣHCH and Σdichloro-diphenyl-trichloroethane (DDT) constituted ~86 % of Σ₂₀OCPs. Isomer ratios indicated fresh usage of lindane, DDT and technical-grade HCH. Toxicological comparison with freshwater sediment quality guidelines showed γ-HCH and DDT at high levels of concern. β-HCH, α-HCH, endrin, heptachlor epoxide, dichloro-diphenyl-dichloroethane (DDD), dichloro-diphenyl-dichloroethylene and chlordane were above some of the guideline levels. TOC and BC had mean concentrations of 1.37?±?0.51 % and 0.46?±?0.23 mg g^?1, respectively. BC constituted 1.25 to 10.56 % of TOC. We observed low to moderate correlations of BC with isomers of HCH, p,p′-DDT and methoxychlor while of TOC with Σ₂₀OCPs, γ-HCH, endosulfan sulfate and methoxychlor. Principal component analysis enabled correlating and clustering of various OCPs, BC and TOC. OCP distribution was related with pH, electrical conductivity, soil moisture and finer fractions of sediment. OCPs with similarity in properties that determine their interactions with carbonaceous components of sediment clustered together. A number of factors may, thus, be involved in the regulation of interactive forces between BC and OCPs. BC in this study may be more important than TOC in the retention of some OCPs into fluvial sediments, thereby reducing their bioavailability. The finding is probably the first of its kind to report and emphasises the role of BC in the persistence of OCPs in fluvial sediments.     

Characterization of carbonaceous aerosols over Delhi in Ganga basin: seasonal variability and possible sources

The mass concentration of carbonaceous species, organic carbon (OC), and elemental carbon (EC) using a semicontinuous thermo-optical EC-OC analyzer, and black carbon (BC) using an Aethalometer were measured simultaneously at an urban mega city Delhi in Ganga basin from January 2011 to May 2012. The concentrations of OC, EC, and BC exhibit seasonal variability, and their concentrations were ～2 times higher during winter (OC 38.1?±?17.9 μg m^?3, EC 15.8?±?7.3 μg m^?3, and BC 10.1?±?5.3 μg m^?3) compared to those in summer (OC 14.1?±?4.3 μg m^?3, EC 7.5?±?1.5 μg m^?3, and BC 4.9?±?1.5 μg m^?3). A significant correlation between OC and EC (R?=?0.95, n?=?232) indicate their common emission sources with relatively lower OC/EC ratio (range 1.0–3.6, mean 2.2?±?0.5) suggests fossil fuel emission as a major source of carbonaceous aerosols over the station. On average, mass concentration of EC was found to be ～38 % higher than BC during the study period. The measured absorption coefficient (b_abs) was significantly correlated with EC, suggesting EC as a major absorbing species in ambient aerosols at Delhi. Furthermore, the estimated mass absorption efficiency (σ_abs) values are similar during winter (5.0?±?1.5 m² g^?1) and summer (4.8?±?2.8 m² g^?1). Significantly high aerosol loading of carbonaceous species emphasize an urgent need to focus on air quality management and proper impact assessment on health perspective in these regions.     

Sorption of perfluorooctane sulfonate to carbon nanotubes in aquatic sediments

To date, sorption of organic compounds to nanomaterials has mainly been studied for the nanomaterial in its pristine state. However, sorption may be different when nanomaterials are buried in sediments. Here, we studied sorption of Perfluorooctane sulfonate (PFOS) to sediment and to sediment with 4% multiwalled carbon nanotubes (MWCNTs), as a function of factors affecting PFOS sorption; aqueous concentration, pH and Ca²⁺ concentration. Sorption to MWCNT in the sediment–MWCNT mixtures was assessed by subtracting the contribution of PFOS sorption to sediment-only from PFOS sorption to the total sediment–MWCNT mixture. PFOS Log K_D values ranged 0.52–1.62 L kg^?1 for sediment and 1.91–2.90 L kg^?1 for MWCNT present in the sediment. The latter values are relatively low, which is attributed to fouling of MWCNT by sediment organic matter. PFOS sorption was near-linear for sediment (Freundlich exponent of 0.92 ± 0.063) but non-linear for MWCNT (Freundlich exponent of 0.66 ± 0.03). Consequently, the impact of MWCNT on sorption in the mixture was larger at low PFOS aqueous concentration. Effects of pH and Ca²⁺ on PFOS sorption to MWCNT were statistically significant. We conclude that MWCNT fouling and PFOS concentration dependency are important factors affecting PFOS–MWCNT interactions in sediments.     

Sorption of PAHs and PCBs to activated carbon: coal versus biomass-based quality

The addition of activated carbon (AC) is an increasingly popular method for pollutant immobilization, and the AC material can be made of biomass or coal/fossil feedstock. The aim of the present study was to investigate whether there are differences between pollutant sorption to biomass and coal-based AC in the presence and absence of sediment. Through N₂ and CO₂ adsorption to probe surface area and pore size it was shown that the biomass-based AC had a stronger dominance of narrow pores in the size range 3.5-15 Å than the anthracite-based material. In the absence of sediment, sorption isotherms for the probe compounds pyrene and PCB-101 showed stronger sorption for the biomass-based AC (logarithmic Freundlich coefficients 8.15 for pyrene; 9.91 for PCB-101) than for the anthracite-based one (logarithmic Freundlich coefficients 7.20 and 9.70, respectively). In the presence of sediment, the opposite trend was observed, with the stronger sorption for anthracite-based AC. Thus, the presence of competing and/or pore-blocking sediment constituents reduces sorption to a larger extent for biomass-derived AC (factor of 5 for pyrene to almost 100 for PCB-101) than for anthracite-based AC (no reduction for pyrene to factor of 5 for PCB-101). This difference is tentatively attributed to the difference in pore size distribution, narrow pores being more prone to clogging, and could have implications for remediation feasibility with AC from different sources.     

Modifications of black carbons and their influence on pyrene sorption

Sorption of pyrene on black carbons (BCs) obtained by heating sawdust at two temperatures (400 and 700 °C, denoted as 400BC and 700BC, respectively), as well as on modified BCs (via oxidation, oximation, and hydrolysis) was studied to investigate the role of BC structural characteristics in sorption of hydrophobic organic compounds. Pyrene was bound strongly by 700BC and 400BC, with organic carbon normalized distribution coefficients (K_oc) of 10^5.04-10^5.86 and 10^4.65-10^5.16, respectively, at equilibrium pyrene concentrations of 10-100 μg L⁻¹. Both chemical composition and pore distribution of the two BCs changed after modifications, which led to changes in their sorption characteristics for pyrene. After modifications, the linearity of pyrene sorption isotherm increased for 700BC but decreased for 400BC. For 700BC, both oxidation and oximation reduced pyrene sorption, with K_oc decreasing by 69.1-73.7% and 18.7-33.9%, respectively, whereas hydrolysis did not exert a significant influence. For 400BC, oxidation and hydrolysis reduced K_oc by 2.28-25.9% and 29.2-33.9%, respectively, while oximation increased K_oc. In most cases, the change in sorption capacity could be explained by the changes in C content and type, polarity, surface area, and micropore volume of the BCs; however, the role of conformation (the accessibility to sorption sites) could not be ignored.     

Sorption of organic pollutants by marine sediments: implication for the role of particulate organic matter

The objective of this study was to quantify sorption properties for kerogen/black carbon (BC)-bearing sediments. Single-solute sorption isotherms were measured for five pristine marine sediments using phenanthrene, naphthalene, 1,3,5-trichlorobenzene, and 1,4-dichlorobenzene as the sorbates. The results showed that the sorption isotherms were nonlinear and that the organic carbon normalized single point K_OC values were comparable to those reported in the literature for the purified keorgen and BC, but are much higher than the data reported for HA and kerogen/BC-containing terrestrial soils and sediments. It is likely that koergen and BC associated with these pristine marine sediments may not be encapsulated with humic acids or Fe and Mn oxides and hydroxides as often do in terrestrial soils and sediments. As a result, they may be fully accessible to sorbing molecules, exhibiting higher sorption capacities. The study suggests that competition from background HOCs and reduced accessibility when kerogen and BC are associated with terrestrial sediments may dramatically increase variability of sorption reactivities of geosorbents. Such variability may lead to large uncertainties in the prediction of sorption from the contents of kerogen and/or BC along with TOC.     

Effect of sediment properties on the sorption of C12-2-LAS in marine and estuarine sediments

Linear alkylbenzene sulfonates (LAS) are anionic high production volume surfactants used in the manufacture of cleaning products. Here, we have studied the effect of the characteristics of marine and estuarine sediments on the sorption of LAS. Sorption experiments were performed with single sediment materials (pure clays and sea sand), with sediments treated to reduce their organic carbon content, and with field marine and estuarine sediments. C₁₂-2-LAS was used as a model compound. Sorption to the clays montmorillonite and kaolinite resulted in non-linear isotherms very similar for both clays. When reducing the organic content, sorption coefficients decreased proportionally to the fraction removed in fine grain sediments but this was not the case for the sandy sediment. The correlation of the sediment characteristics with the sorption coefficients at different surfactant concentrations showed that at concentrations below 10 μg C₁₂-2-LAS/L, the clay content correlated better with sorption, while the organic fraction became more significant at higher concentrations.     

Sorption of alkylphenols on Ebro River sediments: comparing isotherms with field observations in river water and sediments

This study reports sorption isotherms of the endocrine disruptors nonylphenol (NP) and octylphenol (OP) in three sediment samples from the Ebro River basin (NE Spain), with organic carbon fractions (f_OC) ranging from 0.0035 to 0.082 g_OC g⁻¹. All isotherms were fitted to the Freundlich model with slightly nonlinear exponents ranging from 0.80 to 0.94. The solubility of the compounds as well as the organic carbon (OC) content had the strongest influences on the sorption behavior of these compounds. Comparison of the laboratory-spiked samples with the native contamination of NP of 45 water and concurrent sediment samples resulted in reasonable matches between both data sets, even though the lowest concentrations in the field were not completely reached in laboratory tests. This good agreement indicates that sorption laboratory data can be extrapolated to environmental levels and therefore the distribution of nonylphenol between sediments and water can be predicted with a precision of one order of magnitude. Furthermore, laboratory experiments with simultaneous loading of NP and OP revealed negligible competition for sorption sites at low concentrations.     

Effect of soil and sediment composition on acetochlor sorption and desorption

Background, aim, and scope  Herbicide fate and its transport in soils and sediments greatly depend upon sorption–desorption processes. Quantitative determination of herbicide sorption–desorption is therefore essential for both the understanding of transport and the sorption equilibrium in the soil/sediment–water system; and it is also an important parameter for predicting herbicide fate using mathematical simulation models. The total soil/sediment organic carbon content and its qualitative characteristics are the most important factors affecting sorption–desorption of herbicides in soil or sediment. Since the acetochlor is one of the most frequently used herbicides in Slovakia to control annual grasses and certain annual broad-leaved weeds in maize and potatoes, and posses various negative health effects on human beings, our aim in this study was to investigate acetochlor sorption and desorption in various soil/sediment samples from Slovakia. The main soil/sediment characteristics governing acetochlor sorption–desorption were also identified. Materials and methods  The sorption–desorption of acetochlor, using the batch equilibration method, was studied on eight surface soils, one subsurface soil and five sediments collected from the Laborec River and three water reservoirs. Soils and sediments were characterized by commonly used methods for their total organic carbon content, distribution of humus components, pH, grain-size distribution, and smectite content, and for calcium carbonate content. The effect of soil/sediment characteristics on acetochlor sorption–desorption was examined by simple correlation analysis. Results  Sorption of acetochlor was expressed as the distribution coefficient (K _d). K _d values slightly decreased as the initial acetochlor concentration increased. These values indicated that acetochlor was moderately sorbed by soils and sediments. Highly significant correlations between the K _d values and the organic carbon content were observed at both initial concentrations. However, sorption of acetochlor was most closely correlated to the humic acid carbon, and less to the fulvic acid carbon. The total organic carbon content was found to also significantly influence acetochlor desorption. Discussion  Since the strong linear relationship between the K _d values of acetochlor and the organic carbon content was already released, the corresponding K _oc values were calculated. Considerable variation in the K _oc values suggested that other soil/sediment parameters besides the total soil organic carbon content could be involved in acetochlor sorption. This was revealed by a significant correlation between the K _oc values and the ratio of humic acid carbon to fulvic acid carbon (C_HA/C_FA). Conclusions  When comparing acetochlor sorption in a range of soils and sediments, different K _d values which are strongly correlated to the total organic carbon content were found. Concerning the humus fractions, the humic acid carbon content was strongly correlated to the K _d values, and it is therefore a better predictor of the acetochlor sorption than the total organic carbon content. Variation in the K _oc values was attributed to the differences in distribution of humus components between soils and sediments. Desorption of acetochlor was significantly influenced by total organic carbon content, with a greater organic carbon content reducing desorption. Recommendations and perspectives  This study examined the sorption–desorption processes of acetochlor in soils and sediments. The obtained sorption data are important for qualitative assessment of acetochlor mobility in natural solids, but further studies must be carried out to understand its environmental fate and transport more thoroughly. Although, the total organic carbon content, the humus fractions of the organic matter and the C_HA/C_FA ratio were sufficient predictors of the acetochlor sorption–desorption. Further investigations of the structural and chemical characteristics of humic substances derived from different origins are necessary to more preciously explain differences in acetochlor sorption in the soils and sediments observed in this study.     

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.     

Sources and characteristics of carbonaceous aerosols at Agra “World heritage site” and Delhi “capital city of India”

Agra, one of the oldest cities “World Heritage site”, and Delhi, the capital city of India are both located in the border of Indo-Gangetic Plains (IGP) and heavily loaded with atmospheric aerosols due to tourist place, anthropogenic activities, and its topography, respectively. Therefore, there is need for monitoring of atmospheric aerosols to perceive the scenario and effects of particles over northern part of India. The present study was carried out at Agra (AGR) as well as Delhi (DEL) during winter period from November 2011 to February 2012 of fine particulate (PM_2.5: d?<?2.5 μm) as well as associated carbonaceous aerosols. PM_2.5 was collected at both places using medium volume air sampler (offline measurement) and analyzed for organic carbon (OC) and elemental carbon (EC). Also, simultaneously, black carbon (BC) was measured (online) at DEL. The average mass concentration of PM_2.5 was 165.42?±?119.46 μg m^?3 at AGR while at DEL it was 211.67?±?41.94 μg m^?3 which is ~27 % higher at DEL than AGR whereas the BC mass concentration was 10.60 μg m^?3. The PM_2.5 was substantially higher than the annual standard stipulated by central pollution control board and United States Environmental Protection Agency standards. The average concentrations of OC and EC were 69.96?±?34.42 and 9.53?±?7.27 μm m^?3, respectively. Total carbon (TC) was 79.01?±?38.98 μg m^?3 at AGR, while it was 50.11?±?11.93 (OC), 10.67?±?3.56 μg m^?3 (EC), and 60.78?±?14.56 μg m^?3 (TC) at DEL. The OC/EC ratio was 13.75 at (AGR) and 5.45 at (DEL). The higher OC/EC ratio at Agra indicates that the formation of secondary organic aerosol which emitted from variable primary sources. Significant correlation between PM_2.5 and its carbonaceous species were observed indicating similarity in sources at both sites. The average concentrations of secondary organic carbon (SOC) and primary organic carbon (POC) at AGR were 48.16 and 26.52 μg m^?3 while at DEL it was 38.78 and 27.55 μg m^?3, respectively. In the case of POC, similar concentrations were observed at both places but in the case of SOC higher over AGR by 24 in comparison to DEL, it is due to the high concentration of OC over AGR. Secondary organic aerosol (SOA) was 42 % higher at AGR than DEL which confirms the formation of secondary aerosol at AGR due to rural environment with higher concentrations of coarse mode particles. The SOA contribution in PM_2.5 was also estimated and was ~32 and 12 % at AGR and DEL respectively. Being high loading of fine particles along with carbonaceous aerosol, it is suggested to take necessary and immediate action in mitigation of the emission of carbonaceous aerosol in the northern part of India.     

Studies on the sorption behaviors of nitrobenzene on marine sediments

The sorption behaviors of nitrobenzene on marine sediments were systematically investigated in this study. The nitrobenzene sorption on both HCl-treated and untreated sediments accorded well with the linear sorption isotherm. It occurred primarily through partition function of organic carbon of sediments. In comparison, the sorption behavior of nitrobenzene on H2O2-treated sediments was nonlinear and conformed to Langmuir isotherm. Sorption of nitrobenzene on H2O2-treated sediment was mainly through surface function of sediment minerals such as clays. With the increase of ionic strength (salinity), solubility of nitrobenzene in solution would decrease. At the same time, the release of dissolvable part of organic carbon into water solution would also decrease. As a result, partition coefficient and saturate adsorption amount of nitrobenzene on marine sediments increased with increasing salinity of seawater. Contrary to the influence of salinity, partition coefficient and saturate adsorption amount of nitrobenzene decreased with increasing temperature.     

The impact of vegetation on sedimentary organic matter composition and PAH desorption

Relationships between sedimentary organic matter (SOM) composition and PAH desorption behavior were determined for vegetated and non-vegetated refinery distillate waste sediments. Sediments were fractionated into size, density, and humin fractions and analyzed for their organic matter content. Bulk sediment and humin fractions differed more in organic matter composition than size/density fractions. Vegetated humin and bulk sediments contained more polar organic carbon, black carbon, and modern (plant) carbon than non-vegetated sediment fractions. Desorption kinetics of phenanthrene, pyrene, chrysene, and C₃-phenanthrene/anthracenes from humin and bulk sediments were investigated using Tenax^® beads and a two-compartment, first-order kinetic model. PAH desorption from distillate waste sediments appeared to be controlled by the slow desorbing fractions of sediment; rate constants were similar to literature values for k_slow and k_{very slow}. After several decades of plant colonization and growth (Phragmites australis), vegetated sediment fractions more extensively desorbed PAHs and had faster desorption kinetics than non-vegetated sediment fractions.     

Sorption of selected pesticides on soils,sediment and straw from a constructed agricultural drainage ditch or pond

Buffer zones such as ponds and ditches are used to reduce field-scale losses of pesticides from subsurface drainage waters to surface waters. The objective of this study was to assess the efficiency of these buffer zones, in particular constructed wetlands, focusing specifically on sorption processes. We modelled the sorption processes of three herbicides [2-methyl-4-chlorophenoxyacetic acid (2,4-MCPA), isoproturon and napropamide] and three fungicides (boscalid, prochloraz and tebuconazole) on four substrates (two soils, sediment and straw) commonly found in a pond and ditch in Lorraine (France). A wide range of Freundlich coefficient (K _fads) values was obtained, from 0.74 to 442.63 mg^1???n ?L ⁿ ?kg^?1, and the corresponding K _foc values ranged from 56 to 3,725 mg^1???n ?L ⁿ ?kg^?1. Based on potential retention, the substrates may be classified as straw >> sediments > soils. These results show the importance of organic carbon content and nature in the process of sorption. Similarly, the studied pesticides could be classified according to their adsorption capacity as follows: prochloraz >> tebuconazole–boscalid > napropamide >> MCPA–isoproturon. This classification is strongly influenced by the physico-chemical properties of pesticides, especially solubility and K _oc. Straw exhibited the largest quantity of non-desorbable pesticide residues, from 12.1 to 224.2 mg/L for all pesticides. The presence of plants could increase soil–sediment sorption capacity. Thus, establishment and maintenance of plants and straw filters should be promoted to optimise sorption processes and the efficiency of ponds and ditches in reducing surface water pollution.     

Sorption of 17α-ethinyl estradiol, bisphenol A and phenanthrene to different size fractions of soil and sediment

The potential for negative effects caused by endocrine disrupting chemicals (EDCs) release into the environment is a prominent concern and numerous research projects have investigated possible environmental fate and toxicity. However, their sorption behavior by size fractions of soil and sediment has not been systematically represented. The sorption of bisphenol A (BPA), 17α-ethinyl estradiol (EE2) and phenanthrene (Phen) by different size fractions of soil and sediment were investigated. Sorption isotherms of EE2, BPA, and Phen by size fractions of soil (SL) and sediment (ST) were well fitted to the Freundlich model. The positive correlation between EE2, BPA and Phen sorption capacity (log K_d) of size fractions and their organic carbon (OC) content suggests that OC of size fractions in SL and ST should regulate sorption, while the surface area (SA) of size fractions may not account for sorption of EE2, BPA and Phen. Each size fraction of ST had higher sorption capacity (K_d or K_OC) of EE2 and BPA than that of SL due to their difference in the polarity of organic matter (OM) between terrestrial and aquatic sources. Sorption capacity logK_d for size fractions of SL and ST did not follow the order: clay > silt > sand due to the difference in OM abundance and composition between the size fractions. Large particle fractions of ST contributed about 80% to the overall sorption for any EE2, BPA, and Phen. This study was significant to evaluate size fractions of soil and sediment as well as their associated OM affecting EE2 and BPA sorption processes.     

Potassium-based sorbents from fly ash for high-temperature CO<Subscript>2</Subscript> capture

Potassium-fly ash (K-FA) sorbents were investigated for high-temperature CO₂ sorption. K-FAs were synthesised using coal fly ash as source of silica and aluminium. The synthesised materials were also mixed with Li₂CO₃ and Ca(OH)₂ to evaluate their effect on CO₂ capture. Temperature strongly affected the performance of the K-FA sorbents, resulting in a CO₂ uptake of 1.45 mmol CO₂/g sorbent for K-FA 1:1 at 700 °C. The CO₂ sorption was enhanced by the presence of Li₂CO₃ (10 wt%), with the K-FA 1:1 capturing 2.38 mmol CO₂/g sorbent at 700 °C in 5 min. This sorption was found to be similar to previously developed Li-Na-FA (2.54 mmol/g) and Li-FA (2.4 mmol/g) sorbents. The presence of 10 % Li₂CO₃ also accelerated sorption and desorption. The results suggest that the increased uptake of CO₂ and faster reaction rates in presence of K-FA can be ascribed to the formation of K-Li eutectic phase, which favours the diffusion of potassium and CO₂ in the material matrix. The cyclic experiments showed that the K-FA materials maintained stable CO₂ uptake and reaction rates over 10 cycles.     

Black carbon-dominated PCDD/Fs sorption to soils at a former wood impregnation site

The influence of black carbon (BC) on the sorption of 17 native polychlorinated-p-dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was studied in five soil samples from a sawmill site where wood used to be impregnated with chlorophenol preservatives. The presence of BC caused measured total organic carbon (TOC)-water distribution ratios (K(TOC)) to be a median factor of 51 (interquartile range 18-68, n=85) higher than modeled amorphous organic carbon (AOC)-water distribution ratios (K(AOC)). K(TOC) was a factor of 73+/-27 above K(AOC) for PCDFs (n=10) and a factor of 20+/-13 (n=7) for PCDDs. The reason for this difference is probably that attaining a planar configuration after sorption to BC is less thermodynamically favorable for PCDDs than for PCDFs. BC-water distribution ratios were calculated from K(TOC), K(AOC) and BC contents, and ranged from 10(9.9) (2,3,7,8-Tetra-CDD) to 10(11.5) l kg(-1) (Octa-CDF). More than 90% of the PCDD/Fs in the soil was calculated to be BC-sorbed. Dissolved organic carbon (DOC)-water distribution ratios were measured to be in the same order of magnitude as K(AOC). This study shows that strong sorption to BC should be included when assessing ecotoxicological risk or modeling transport to groundwater of PCDD/Fs in soil.