The role of sorption and bacteria in mercury partitioning and bioavailability in artificial sediments

This study compared the relative importance of three types of sorption (organic matter-particle, mercury-organic matter and mercury-particle) in controlling the overall mercury partitioning and bioavailability in sediments. We found that all three types of sorption were important for both inorganic mercury (Hg) and methylated mercury (MeHg). Mercury-particle sorption was more important than mercury-fulvic acid (FA) sorption in increasing the mercury concentrations with increasing aging. Bioavailability (quantified by gut juice extraction from sipunculans) was mainly controlled by mercury-particle sorption, while FA-particle and mercury-FA sorption were not as important, especially for MeHg. Bacterial activity also increased the partitioning of Hg or MeHg in the sediments and was further facilitated by the presence of organic matter. The bioavailability of Hg or MeHg from sediments was only slightly influenced by bacterial activity. This study highlights the importance of sorption from various sources (especially mercury-particle sorption) as well as bacteria in controlling the partitioning and bioavailability of Hg or MeHg in sediments.     

Sorption of naphthalene and phenanthrene by soil humic acids

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

Sorption of mercury (II) in Amazon soils from column studies

The sorption of Hg (II) onto four different types of Amazon soils from the A-horizon was investigated by means of column experiments under saturation conditions and controlled metal load. Higher organic matter contents in the soil resulted in higher Hg (II) adsorptions, reaching values as high as 3.8 mg Hg g⁻¹ soil. The amount of mercury adsorbed on a soil column (Q) shows a very poor correlation with soil clay content (r² = 0.2527), indicating that Hg sorption in these topsoil samples is chiefly governed by the organic matter content. Desorption experiments using Negro River (Amazon) waters were conducted using soil saturated with Hg (II) in order to better understand the metal leaching mechanism. The amount of Hg (II) released from soils was around 30% of the total sorbed mercury upon saturation, suggesting that mercury sorption in the soils present in the catchment area of the Negro River basin is not a reversible process.     

Suitability of dye-clay complexes for removal of non-ionic organic compounds from aqueous solutions

Aqueous sorption of phenol, atrazine and naphthalene was measured on complexes formed from Na-montmorillonite (Fischer bentonite) and the organic cationic dyes crystal violet and rhodamine-B. Sorption isotherms were found to be non-linear. This agrees well with the rigid nature of the dye-clay organic coverage, which provides a finite surface for adsorption. High values of organic carbon-normalized distribution coefficients reached 20,000-25,000 for atrazine on rhodamine-B-montmorillonite, 7000 for atrazine on crystal violet-montmorillonite, and 1500 for phenol on crystal violet-montmorillonite. As such, dye-clays may significantly extend the variety of organoclay sorbents that effectively reduce aqueous concentrations of non-ionic organic compounds.     

Environmental labeling of car tires--toxicity to Daphnia magna can be used as a screening method

Car tires contain several water-soluble compounds that can leach into water and have toxic effects on aquatic organisms. Due to tire wear, 10,000 tonnes of rubber particles end up along the Swedish roads every year. This leads to a diffuse input of emissions of several compounds. Emissions of polyaromatic hydrocarbons (PAHs) are of particular concern. PAHs are ingredients of the high aromatic oil (HA oil) that is used in the rubber as a softener and as a filler. The exclusion of HA oils from car tires has started, and an environmental labeling of tires could make HA oils obsolete. The toxicity to Daphnia magna from 12 randomly selected car tires was tested in this study. Rubber from the tread of the tires was grated into small pieces, to simulate material from tire wear, and the rubber was equilibrated with dilution water for 72 h before addition of test organisms. The 24-h EC50s of the rubber pieces ranged from 0.29 to 32 gl-1, and the 48-h EC50s ranged from 0.0625 to 2.41 gl-1. Summer tires were more toxic than winter tires. After the 48-h exposure, the daphnids were exposed to UV-light for 2 h, to determine if the tires contained compounds that were phototoxic. After UV-activation the EC50s ranged from 0.0625 to 0.38 gl-1. Four of the 12 tires had a very distinct photoactivation, with a toxicity increase of >10 times. This study has shown that the used method for toxicity testing with Daphnia magna according to ISO 6341 could be used as a basis for environmental labeling of car tires.     

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

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

Soils impacted by PAHs: Would the stabilized organic matter be a green tool for the immobilization of these noxious compounds?

The objective of this study was to investigate the role of stabilized organic matter (vermicompost) and tropical soils in the sorption of naphthalene, anthracene and benzo[a]pyrene. The results obtained for the three compounds were extrapolated for the priority polycyclic aromatic hydrocarbons (PAHs) pollutants according to Environmental Protection Agency (US EPA). To evaluate the sorption process, high performance liquid chromatography was employed and the data was fitted by Freundlich isotherms. The results suggest that the sorption effect generally increases with the number of benzene rings of the PAHs, and that the persistence of PAHs in the environment is possibly related to the number of benzene rings in the PAH molecule. In addition, the pH of the vermicompost can strongly affect the adsorption process in this matrix.     

Biochar as low-cost sorbent of volatile fuel organic compounds: potential application to water remediation

Pyrolysis of waste materials to produce biochar is an excellent and suitable alternative supporting a circular bio-based economy. One of the properties attributed to biochar is the capacity for sorbing organic contaminants, which is determined by its composition and physicochemical characteristics. In this study, the capacity of waste-derived biochar to retain volatile fuel organic compounds (benzene, toluene, ethylbenzene and xylene (BTEX) and fuel oxygenates (FO)) from artificially contaminated water was assessed using batch-based sorption experiments. Additionally, the sorption isotherms were established. The results showed significant differences between BTEX and FO sorption on biochar, being the most hydrophobic and non-polar contaminants those showing the highest retention. Furthermore, the sorption process reflected a multilayer behaviour and a relatively high sorption capacity of the biochar materials. Langmuir and Freundlich models were adequate to describe the experimental results and to detect general differences in the sorption behaviour of volatile fuel organic compounds. It was also observed that the feedstock material and biochar pyrolysis conditions had a significant influence in the sorption process. The highest sorption capacity was found in biochars produced at high temperature (>?400 °C) and thus rich in aromatic C, such as eucalyptus and corn cob biochars. Overall, waste-derived biochar offers a viable alternative to be used in the remediation of volatile fuel organic compounds from water due to its high sorption capacity.

     

Acute toxicity of leachates of tire wear material to Daphnia magna--variability and toxic components

Large amounts of tire rubber are deposited along the roads due to tread wear. Several compounds may leach from the rubber and cause toxicity to aquatic organisms. To investigate the toxic effects of tire wear material from different tires, rubber was abraded from the treads of twenty-five tires. Leachates were prepared by allowing the rubber to equilibrate with dilution water at 44 degrees C for 72 h. Then the rubber was filtered from the leachates, and test organisms (Daphnia magna) were added. Forty-eight hour EC50s ranged from 0.5 to >10.0 g l(-1). The toxicity identification evaluation (TIE) indicated that non-polar organic compounds caused most of the toxicity. UV exposure of the filtered tire leachates caused no significant increase in toxicity. However, when tested as unfiltered leachates (the rubber was not filtered from the leachates before addition of D. magna) photo-enhanced toxicity was considerable for some tires, which means that test procedures are important when testing tire leachates for aquatic (photo) toxicity. The acute toxicity of tire wear for Daphnia magna was found to be <40 times a predicted environmental concentration based on reports on the concentration of a tire component found in environmental samples, which emphasizes the need for a more extensive risk assessment of tire wear for the environment.     

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

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

改性钙铝LDH对水中硝基苯和萘的吸附

为了解经十二烷基硫酸钠（SDS）改性的钙铝LDH作为吸附剂吸附水体中硝基苯和萘的吸附性能,结合有机钙铝LDH的结构特征和有机质含量,对有机改性前后钙铝LDH分别对硝基苯、萘的动力学和等温吸附线进行了研究。探讨了其吸附机理。结果表明,有机钙铝LDH层间距为3．25nm,有机质含量约为45％。提出了有机改性后的钙铝LDH对硝基苯和萘的吸附率增强,且萘的吸附效率高于硝基苯;有机钙铝LDH对非离子型有机污染物的吸附作用机理主要为分配作用。     

Sorption of heterocyclic compounds from a complex mixture of coal-tar compounds on natural clayey till

The sorption and desorption of heterocyclic organic compounds in a complex multisolute system to a natural clayey till was investigated. The composition of the solutes reflect a simplified composition of an aqueous phase in contact with coal tar. Sorption was studied for two ratios (s:l) of clayey till (solid) to aqueous phase (liquid). The effect of the complex mixture of solutes on sorption of the four heterocyclic compounds: benzofuran, dibenzofuran, benzothiophene, and dibenzothiophene is evaluated by comparison with their sorption measured in single-solute systems. Sorption of the four compounds is affected by the complex mixture, with sorption decreases for all four compounds at high s:l ratio indicating competitive sorption. The effect on sorption of the individual compounds is not related to solubility or hydrophobicity of the compounds. Freundlich-type isotherms are observed for all compounds in the high s:l-ratio experiments, but for the most hydrophobic compounds isotherms are close to linear. The sorption of N-compounds and benzofuran is apparently influenced by cation exchange and dipole–dipole attraction to clay minerals. At high concentrations a dramatic increase in the sorption of the most strongly sorbing compounds is observed in the low s:l-ratio experiment. The dramatic increase in sorption appears to be a result of multimolecular layer sorption or condensation on surfaces in the clayey till at high surface density of organic compounds, and the data are fitted by BET (Brunauer, Emmet, and Teller) type 2 isotherms. The increase may or may not be induced by the presence of N-heterocyclic compounds sorbed by cation exchange and dipole–dipole attraction. The desorption of the compounds was studied for the low s:l ratio where multimolecular layer formation apparently had occurred. Partially irreversible sorption, hysteric Langmuir type desorption with isotherms of very high K_l coefficient, or behaviour reflecting dissolution of a condensed phase is observed.     

有机污染物湿地生物降解实验规律研究

本文以苯、甲苯和萘为对象 ,通过实验研究 ,测定有机污染物的土壤 水吸附平衡过程、在水溶液中生物降解过程以及在湿地系统 (即土壤 水 微生物系统 )中生物降解过程 ,并以质量守恒定律为基础 ,建立有机污染物湿地生物降解过程综合数学模型 ;数学模型通过实验验证。利用模型 ,定量预测了污染物生物降解所需的时间和程度 ,并提出动力学因子FK,判断污染物湿地生物降解速度的控制因素 ,定量预测了污染物在土壤固相的浓度分布规律     

Displacement and competitive sorption of organic pollutants on multiwalled carbon nanotubes

Displacement of lindane presorbed on the pristine and OH-functionalized multiwalled carbon nanotubes (MWCNTs) by phenanthrene, naphthalene, and atrazine, and competition of these compounds with lindane on the aforementioned sorbents were investigated. Displacement of lindane presorbed on MWCNTs by atrazine, naphthalene, and phenanthrene, and competitive sorption effect of these chemicals with lindane on MWCNTs followed the same order: atrazine > naphthalene > phenanthrene. The lowest competition and displacement of lindane by phenanthrene were mainly because of the strong interactions between these two chemicals, whereas interaction of lindane with atrazine and naphthalene was quite low. The more pronounced displacement of lindane by atrazine than naphthalene and higher competitive sorption of lindane with atrazine than with naphthalene can be ascribed to the larger molecular volume of atrazine; thus, the steric hindrance effect is higher relative to naphthalene. This study is valuable for evaluating influence of the coexisting organic compounds on sorption of primary solute towards MWCNTs in the environment.     

Sorption of apolar and polar organic contaminants by waste tire rubber and its chars in single- and bi-solute systems

Single- and bi-solute sorption of organic compounds [1,3-dichlorbenzene (DCB), 1,3-dinitrobenzene (DNB) and 2,4-dichlorophenol (DCP)] on ground tire rubber and its chars was studied. The chars were prepared by pyrolyzing tire rubber at different temperatures (200-800 °C). Their surface area, aromaticity and hydrophobicity increase greatly with pyrolytic temperature, and the polymeric phase is partly converted into a condensed phase. The sorption of DNB and DCP increases with pyrolytic temperature and is characterized by a transition from a partition dominant to an adsorption dominant process. However, the sorption of DCB linearly decreases with the pyrolytic temperature. The enhanced adsorption of DNB and DCP on carbonized phase is primarily attributed to nonhydrophobic interactions such as π-π electron-donor-acceptor interactions and/or H bonding. The higher partition of DCB to polymeric phase is attributed to its high hydrophobicity. Competitive sorption between DCB and DCP on the tire chars is highly dependent on dissociation of the latter.     

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.     

Carbon and hydrogen isotope effects during sorption of organic contaminants on carbonaceous materials

Stable carbon and hydrogen isotopes can be an efficient means to validate biodegradation of organic contaminants in groundwater since it results in an isotopic fractionation. A prerequisite in applying this method in the field is the proof that other processes decreasing the contaminant concentration are conservative with respect to isotope effects. In this paper we show for carbon isotopes of halogenated hydrocarbon compounds [trichloroethene (TCE), cis-dichloroethene (c-DCE), vinylchloride (VC)] and carbon and hydrogen isotopes of BTEX compounds (benzene, toluene, p-xylene) that no significant fractionation occurs during equilibrium sorption onto activated carbon, lignite coke and lignite. In general, effects were in the range of the reproducibility limit of the analytical instrument (0.5 per thousand for delta13C, and 8 per thousand for delta2H). This observation was made for fractions sorbed of less than 5% to more than 95%. Also for rate-limited sorption of TCE onto activated carbon, no significant fractionation in carbon isotopes could be observed. These findings support the assumption that for these classes of compounds, sorption processes in aquifer systems are conservative with respect to isotope effects.     

Mercury sorption to sediments: dependence on grain size, dissolved organic carbon, and suspended bacteria

A combination of laboratory scale derived correlations and measurements of grain size distribution, DOC (dissolved organic carbon) concentration, and density of suspended bacteria promises to be useful in estimating Hg(II) sorption in heterogeneous streambeds and groundwater environments. This was found by shaking intact sediment and fractions thereof (<63-2000mum) with solutions of HgCl(2) (1.0-10.0ngml(-1)). The intact sediment was also shaken with the Hg(II) solutions separately in presence of DOC (6.5-90.2mugml(-1)) or brought in contact with suspensions of a strain of groundwater bacteria (2x10(4)-2x10(6)cellsml(-1)). Hg(II) sorption was rather weak and positively correlated with the grain size, and the sorption coefficient (K(d)) varied between about 300 and 600mlg(-1). By using the relative surface areas of the fractions, K(d) for the intact sediment was back calculated with 2% deviation. K(d) was negatively correlated with the concentration of DOC and positively correlated with the number of bacteria. A multiple regression showed that K(d) was significantly more influenced by the number of bacteria than by the grain size. The findings imply that common DOC concentrations in groundwater and streambeds, 5-20mugml(-1), will halve the K(d) obtained from standard sorption assays of Hg(II), and that K(d) will almost double when the cell numbers are doubled at densities that are common in aquifers. The findings suggest that simultaneous measurements of surface areas of sediment particles, DOC concentrations, and bacterial numbers are useful to predict spatial variation of Hg(II) sorption in aquifers and sandy sediments.     

A reactive transport model for mercury fate in soil—application to different anthropogenic pollution sources

Soil systems are a common receptor of anthropogenic mercury (Hg) contamination. Soils play an important role in the containment or dispersion of pollution to surface water, groundwater or the atmosphere. A one-dimensional model for simulating Hg fate and transport for variably saturated and transient flow conditions is presented. The model is developed using the HP1 code, which couples HYDRUS-1D for the water flow and solute transport to PHREEQC for geochemical reactions. The main processes included are Hg aqueous speciation and complexation, sorption to soil organic matter, dissolution of cinnabar and liquid Hg, and Hg reduction and volatilization. Processes such as atmospheric wet and dry deposition, vegetation litter fall and uptake are neglected because they are less relevant in the case of high Hg concentrations resulting from anthropogenic activities. A test case is presented, assuming a hypothetical sandy soil profile and a simulation time frame of 50 years of daily atmospheric inputs. Mercury fate and transport are simulated for three different sources of Hg (cinnabar, residual liquid mercury or aqueous mercuric chloride), as well as for combinations of these sources. Results are presented and discussed with focus on Hg volatilization to the atmosphere, Hg leaching at the bottom of the soil profile and the remaining Hg in or below the initially contaminated soil layer. In the test case, Hg volatilization was negligible because the reduction of Hg²⁺ to Hg⁰ was inhibited by the low concentration of dissolved Hg. Hg leaching was mainly caused by complexation of Hg²⁺ with thiol groups of dissolved organic matter, because in the geochemical model used, this reaction only had a higher equilibrium constant than the sorption reactions. Immobilization of Hg in the initially polluted horizon was enhanced by Hg²⁺ sorption onto humic and fulvic acids (which are more abundant than thiols). Potential benefits of the model for risk management and remediation of contaminated sites are discussed.     

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

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