Release of colloidal particles in natural porous media by monovalent and divalent cations

We study mobilization of colloidal particles from natural porous media, such as soils and groundwater aquifers. Extensive laboratory scale column experiments of particle release from four different subsurface materials are presented. The important characteristics of the release process are (i) its non-exponential kinetics, (ii) the finite supply of colloidal particles and (iii) the strong dependence of the release kinetic on the nature of the adsorbed cations. Particle release depends most sensitively on the relative saturation of the medium with divalent cations. We propose a mathematic model, which captures all these aspects quantitatively, and can be used to describe the coupling between transport of major cations and the release of colloidal particles. The present experimental investigations as well as the developed modeling framework represent an important step towards the understanding of colloid-facilitated transport phenomena in natural porous media.     

Adsorption of methabenzthiazuron on six allophanic and nonallophanic soils: effect of organic matter amendment

This article reports on methabenzthiazuron [1-(1,3-benzothiazol-2-yl)-1,3-dimethylurea] (MBT) adsorption process on six agricultural allophanic and nonallophanic soils. The effect of amendment with exogenous organic matter was also studied. Adsorption kinetic fits an hyperbolic model. MBT adsorption reached an apparent equilibrium within 2 h and followed a second-order reaction. The maximum adsorbed amounts for natural soils ranged from 32 to 145 microg g(-1). Rate constants were considered relatively low (0.27-1.5 x 10(-4) [microg g(-1)](1-n) s-1); the slow process was attributed to a combined effect of difussion and adsorption. MBT adsorption fits the Freundlich model with r values > or =0.998 at P < or = 0.001 significance levels. Kf and Freundlich exponents (l/n) ranged from 5.3 to 82.1 cm3 g(-1) and from 0.66 to 0.73, respectively. Kf values for soils with a low organic matter content were lower than that obtained from the only typical allophanic soil derived from volcanic ash under study. Lineal regression analysis between Kf and organic matter content of nonallophanic soils gave a correlation coefficient of 0.980 (P = 0.02). Dispersion of Kd values together with close values of K(OM) indicate that organic matter (OM) was the principal component responsible for MBT adsorption in unamended soils. Addition of peat decreased soil pH and increased adsorption capacity for allophanic and nonallophanic soils. Kinetic experiments showed enhancements of Xmax values and lower rate constants.     

Biodegradation of polycyclic aromatic hydrocarbons in the natural waters of the Yellow River: effects of high sediment content on biodegradation

The contamination of polycyclic aromatic hydrocarbons (PAHs) has become one of the major problems in the Yellow River of China. As the Yellow River is the most turbid large river in the world, it remains unknown to which extent the high suspended sediment content in the river may affect the fate and effect of PAHs. Here we report the effect of sediment on biodegradation of chrysene, benzo(a)pyrene and benzo(g,h,i)perylene with phenanthrene as a co-metabolism substrate in natural waters from the Yellow River. Biodegradation kinetics of the PAHs in the river water with various levels of sediment contents were studied in the laboratory by fitting with a biodegradation kinetics model for organic compounds not supporting growth. The results indicated that the biodegradation rates of PAHs increased with the sediment content in the water. When the sediment contents were 0, 4 and 10 g/l, the biodegradation rate constants of chrysene with the initial concentration of 3.80 microg/l were 0.053, 0.084 and 0.111 d(-1), respectively. Further studies suggested the enhanced biodegradation rate in the presence of sediment was caused by the following mechanisms: (1) the population of PAH-degrading bacteria in the water system was found to increase with the sediment content; the bacteria population on sediment phase was far greater than that on water phase during the cultivation process; (2) the sorption of PAHs on the sediment phase was well described by the dual adsorption-partition model. Although the sorption capacity of PAH per unit weight of sediment decreased with the increase of the sediment content, the amount of sorbed PAH increased with the sediment content; and, (3) the desorption of PAHs from the solid phase led to a higher concentration near the water-sediment interface. Since the bacteria were also attached to the interface, this resulted in an increased contact chance between the bacteria and PAHs.     

Sediment pollution and dynamic in the Mar Piccolo of Taranto (southern Italy): insights from bottom sediment traps and surficial sediments

Major and trace element, PAH, and PCB concentrations were measured in surface sediments and particles from sediment traps collected in the First and Second Basin of the Mar Piccolo (Gulf of Taranto) in two periods (June–July and August–September, 2013). The aim of the study was to evaluate pollution degree, sediment transport and particle redistribution dynamic within the area. Results confirm the higher contamination of sediments from the First Basin observed by previous researches, particularly for Cu, Hg, Pb, total PAHs, and total PCBs. Advective transport from the First to the Second Basin appears to be the leading transfer mechanism of particles and adsorbed contaminants, as evidenced by measured fluxes and statistical analyses of contaminant concentrations in surficial sediments and particles from sediment traps. Long-range selective transports of PAHs and microbial anaerobic degradation processes for PCBs have been also observed. These results are limited to a restricted time window but are consistent with the presence of transport fluxes at the bottom of the water column. This mechanism deserves further investigation and monitoring activities, potentially being the main responsible of pollutant delivering to the less contaminated sectors of the Mar Piccolo.     

Removal of sorbed polycyclic aromatic hydrocarbons from soil, sludge and sediment samples using the Fenton's reagent process

The use of the Fenton's reagent process has been investigated for the remediation of environmental matrices contaminated by polycyclic aromatic hydrocarbons (PAHs). Laboratory experiments were first conducted in aqueous solutions, to study the kinetics of oxidation and adsorption of PAHs. Benzo[a]pyrene was more rapidly degraded than adsorbed, while only partial oxidation of fluoranthene occurred. In the case of benzo[b]fluoranthene, its adsorption prevented its oxidation. Besides competition effects between PAHs were found, with slower oxidation of mixtures as compared to single PAH solutions. Apparition of some by-products was observed, and a di-hydroxylated derivative of benzo[a]pyrene could be identified under our conditions. Consequently, application to solid environmental matrices (soil, sludge and sediment samples) was performed using large amounts of reagents. The efficiency of the Fenton treatment was dependent on the matrix characteristics (such as its organic carbon content) and the PAH availability (correlated to the date and level of contamination). However, no pH adjustment was required, as well as no iron addition due to the presence of iron oxides in the solid matrices, suggesting the potential application of Fenton-like treatment for the remediation of PAH-contaminated environmental solids.     

The influence of Sarcocornia fruticosa on retention of PAHs in salt marsh sediments (Sado estuary, Portugal)

Depth concentration profiles of PAHs, organic carbon and dissolved oxygen in non-colonised sediments and sediments colonised by Sarcocornia fruticosa from Mitrena salt marsh (Sado, Portugal) were determined in November 2004 and April 2005. Belowground biomass and PAH levels in below and aboveground material were also determined. In both periods, colonised sediments were oxygenated until 15-cm, rich in organic carbon (max 4.4%) and presented much higher PAH concentrations (max. 7.1 microg g(-1)) than non-colonised sediments (max. 0.55 microg g(-1)). Rooting sediments contained the highest PAH concentrations. The five- and six-ring compounds accounted to 50-75% of the total PAHs in colonised sediments, while only to 30% in non-colonised sediments. The elevated concentrations of PAHs in colonised sediments may be attributed to the transfer of dissolved PAH compounds towards the roots as plant uptake water and subsequent sequestration onto organically rich particles. A phase-partitioning mechanism probably explains the higher retention of the heavier PAHs. In addition oxygenated conditions of the rooting sediments favour the degradation of the lighter PAHs and explain the elevated proportion of the heavier compounds. Below and aboveground materials presented lower PAH concentrations (0.18-0.38 microg g(-1)) than colonised sediments. Only 3- and 4-PAHs were quantified in aboveground material, reflecting either preferential translocation of lighter compounds from roots or atmospheric deposition.     

Some models for the adsorption kinetics of pesticides in soil

Abstract

Three models describing adsorption‐desorption kinetics of pesticides in soil, that could be incorporated into computer programs on pesticide movement in soil, were discussed, The first model involved single first‐order rate equations for adsorption and desorption. Results from an analytical and a numerical solution for local equilibration were compared. Concentration‐time relationships for the solution and adsorbed phases were calculated for different rate constants, initial conditions, and partition ratios at equilibrium. The second model described simultaneous adsorption‐desorption equilibration with two mechanisms, both with their own rate constants. After a comparatively fast equilibration with the first mechanism, there was a gradual increase in extent of overall‐adsorption, accompanied with a shift to greater amounts adsorbed by the second mechanism. With the third model, adsorption equilibration occurred by diffusion into a stagnant region. With diffusion distances ranging from 0.1 to 4.0 cm, the time needed for approach to adsorption equilibrium varied from about 0.25 days to about one year. Some of the possibilities of these models were discussed considering published experimental results.     

Speciation and persistence of doxycycline in the aquatic environment: Characterization in terms of steady state kinetics

The aim of the present work was to establish the kinetics for the degradation of doxycycline in the aquatic environment with a view to arriving at a kinetic model that can be used to predict the persistence of antibiotic with confidence. The degradation of doxycycline in both water and sediment phases of aquatic microcosm experiments, as well as in distilled water control experiments, was studied over a period of 90 days. An initial 21% loss due to adsorption by the sediment was observed in the microcosm experiment soon after charging. Biphasic zero-order linear rates of degradation, attributed to microbial degradation of the free and sediment or colloidal particle-adsorbed antibiotic, were observed for both water phase (2.3 × 10^?2 and 4.5 × 10^?3 μgg^?1 day^?1) and sediment phase (7.9 × 10^?3 and 1.5 × 10^?3 μgg^?1 day^?1) of the microcosm experiment. The covered distilled water control experiment exhibited a monophasic zero-order linear rate (1.9 × 10^?3 μgg^?1 day^?1) attributed to hydrolysis, while the distilled water experiment exposed to natural light exhibited biphasic liner rates attributed to a combination of hydrolysis and photolysis (2.9 × 10^?3 μgg^?1 day^?1) and to microbial degradation (9.8 × 10^?3 μgg^?1 day^?1). A kinetic model that takes into account hydrolysis, photolysis, microbial degradation as well as sorption/desorption by colloidal and sediment particles is presented to account for the observed zero-order kinetics. The implications of the observed kinetics on the persistence of doxycycline in the aquatic environment are discussed.     

Alcohol ethoxylate mixtures in marine sediment: Competition for adsorption sites affects the sorption behaviour of individual homologues

Mineral surfaces form the main sorption phase for alcohol ethoxylates (AEs) in marine sediment. Competition for adsorption sites is investigated for marine sediment and kaolinite clay using simple mixtures of AE homologues. For both sorbents, adsorption sites on mineral surfaces can be effectively blocked by an AE homologue with the strongest adsorption affinity. The strongly adsorbed AE, however, forms a second sorption phase to which weakly adsorbing AE will sorb, forming bilayers. An extended dual-mode model accounts for competition effects, while still based on sorption properties of individual compounds. Competition effects become apparent when total adsorbed concentrations reach ∼10% of the adsorption capacity. Deviations from individual sorption isotherms depend on affinity constants and dissolved homologue composition. Competition will not often occur in contaminated field sediments, with AEs concentrations usually far below the adsorption capacity, but will affect sorption studies, sediment toxicity tests or applications with nonionic surfactant mixtures.     

Labile and non-labile desorption rate constants for 33 PCB congeners from lake sediment suspensions

Lake sediments contaminated with polychlorinated biphenyls (PCBs) were purged using a gas stripping technique to estimate desorption rate constants. Desorption profiles and modeling of the data clearly show a two-step release of PCBs from sediment suspensions that can be described as a labile (fast) release followed by a non-labile (slow) release. Data are summarized by labile and non-labile rate constants and by mass in each phase as a function of suspended solids concentration for twelve pure congeners and nine co-eluting data sets (twenty-one chromatograph peaks total). Labile desorption rate constants range from 113 days(-1) to 1.43 days(-1) for the 100 mg/l sediment suspension, from 67.7 days(-1) to 2.45 days(-1) for the 1000 mg/l sediment suspension, and from 8.41 days(-1) to 0.946 days(-1) for the 5000 mg/l sediment suspension. Labile rate constants consistently decreased with increasing suspended solids, and, in general, decreased with increasing degree of chlorination (reflected in increasing retention time in the chromatogram). No consistent trend was observed for the non-labile rate constants with suspended solids concentration or degree of chlorination. The average non-labile rate constant for the PCB congeners studied here was 0.154 days(-1) (s.d.=0.158; n=63). The distribution between the labile and non-labile phases also failed to indicate dependence on suspended solids concentration, chlorine substitution pattern, or molecular weight of the congener, although the data from the 5000 mg/l suspension consistently contained less labile components. The average distributions (n=63) were 60.1% in the labile phase and 39.9% in the non-labile phase.     

Transformation of carbon tetrachloride by bisulfide treated goethite, hematite, magnetite, and kaolinite

This study investigated the transformation of carbon tetrachloride (CT) by goethite, hematite, magnetite, and kaolinite treated with bisulfide to form coatings of iron monosulfide (FeS) and other Fe(II) species. These coatings contribute to abiotic natural attenuation in anaerobic environments. Batch kinetic experiments were performed under anoxic conditions at pH 8.0. Surface-area-normalized pseudo-first-order rate constants for CT transformation did not differ significantly for the three HS- treated iron oxides, but the rate of CT transformation by bisulfide-treated kaolinite was significantly lower, most likely due to kaolinite's lower iron content. The yield of chloroform (CF) from CT transformation was typically approximately 1%. There was negligible or only slight adsorption of several natural organic matter (NOM) model compounds to the surface of HS- treated goethite, and these compounds had no influence on CT transformation rate constants or CF yields. Juglone, on the other hand, adsorbed to a greater extent, and also significantly influenced the CF yield, increasing it by a factor of approximately 20 for HS- treated hematite. We speculate that juglone or its HS- addition product adsorbed to the mineral surface and acted as a hydrogen atom donor that reacted with the trichloromethyl radical intermediate, increasing the CF yield.     

Irrigation model of bleached Kraft mill wastewater through volcanic soil as a pollutants attenuation process

An irrigation process through volcanic soil columns was evaluated for bleached Kraft mill effluent pollutants retention. The system was designed to remove color and phenolic compounds and a simple kinetic model for determining the global mass transfer coefficient and the adsorption rate constant was used. The results clearly indicate that the global mass transfer coefficient values (K(c)a) and the adsorption rate constants are higher for the irrigation processes onto acidified soil. This means that the pretreatment of washing the volcanic soil with an acid solution has a positive effect on the adsorption rate for both pollutant groups. The enhanced adsorption capacity is partially explained by the activation of the metal oxides present in the soil matrix during the acid washing process. Increasing the flow rate from 1.5 to 2.5 ml/min yielded higher (K(c)a) values and adsorption rate constants for both pollutant groups. For instance, regarding color adsorption onto acidified soil, there is an increment of 43% in the (K(c)a) value for the experiment with a flow rate of 2.5 ml/min. Increasing the porosity of the column from 0.55 to 0.59, yielded a decrease in the (K(c)a) values for color and phenolic compounds adsorption processes. Onto natural soil for example, these decreases reached 21% and 24%, respectively. Therefore, the (K(c)a) value is dependent on both the liquid-phase velocity (external resistance) and the soil fraction in the column (internal resistance); making forced convection and diffusion to be the main transport mechanisms involved in the adsorption process. Analyzing the adsorption rate constants (K(c)a)/m, phenolic compounds and color adsorption rates onto acidified soil of 2.25 x 10(-6) and 2.62 x 10(-6) l/mg min were achieved for experiment 1. These adsorption rates are comparable with other adsorption systems and adsorbent materials.     

Competition for adsorption between added phenanthrene and in situ PAHs in two sediments

A study was performed on the influence of the addition of a relatively large amount of phenanthrene to two in situ contaminated sediments on the fractions of native PAHs in both the slowly desorbing domain and the very slowly desorbing domain in comparison to the undisturbed situation. Added phenanthrene was found to be present in both the slowly desorbing domain and the very slowly desorbing domain. The extent of removal of native PAHs from the very slowly desorbing domain induced by the presence of a large excess of phenanthrene was in line with expectations based on the incubation time and the rate constants for desorption of native PAHs from the very slowly desorbing domain. In contrast, the addition of phenanthrene did not result in a removal of native PAHs from the slowly desorbing domain. This was tentatively explained by assuming that native PAHs in the slowly desorbing domain are at adsorption sites with dimensions specific to each PAH and which are, therefore, less suited to other PAHs.     

A comparison of two techniques for studying sediment desorption kinetics of hydrophobic pollutants

A comparison of two techniques (gaseous purge and vial desorption) for studying the kinetics of desorption of hydrophobic pollutants from natural sediments was conducted using identical, pre-equilibrated pollutant-sediment suspensions. Desorption profiles for the two techniques [for Lindane, Aldrin, 2,2'-dichlorobiphenyl (2,2'-DCB), 4,4'-dichlorobiphenyl (4,4'-DCB), and 2,2',6,6'-tetrachlorobiphenyl (TCB)] were then compared, based on the distribution of pollutant mass between the labile (fast) and non-labile (slow) desorption phases and the release rate constants for each phase of release. The vial desorption technique shows many practical advantages over the gaseous purge technique, including its more realistic mixing conditions, the use of an independent sample for each data point (as opposed to a calculation of a cumulative mass purged at each time point), the fact that the vials constitute a closed system and are therefore less subject to ambient contamination, and the relatively low demands of time and money for the vial technique. No consistent trends in labile rate constants or in pollutant distribution between the labile and non-labile phase were observed between the two techniques. A comparison of kinetic parameters shows much faster non-labile rate constants for the gaseous purge technique, attributed to the violent, continuous agitation employed, which likely disrupted sediment aggregates and oxidized the natural organic matter associated with the sediment. Non-labile rate constants have implications for the long-term fate of compounds adsorbed to repetitively disturbed sediments. This study suggests that the traditionally less popular vial desorption technique may yield more realistic non-labile desorption rate constants.     

Immobilization of lead and cadmium from aqueous solution and contaminated sediment using nano-hydroxyapatite

The effectiveness and mechanism of nano-hydroxyapatite particles (nHAp) in immobilizing Pb and Cd from aqueous solutions and contaminated sediment were investigated. The maximum sorption amount (Q_max) of Pb and Cd in aqueous solution was 1.17 and 0.57 mmol/g. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) surface and depth analysis indicated that dissolution-precipitation is the primary immobilization mechanism for Pb, while surface complexation and intraparticle diffusion account for Cd sequestration. Different amounts of nHAp (0-10% nHAp/dry weight) were added to the contaminated sediment. Sequential extraction showed that nHAp could effectively reduce the exchangeable fraction of Pb and Cd in the sediment and significantly reduce the concentration in porewater. The results in this study showed that nHAp can immobilize Pb and Cd in sediment effectively.     

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.     

Uptake of polycyclic aromatic hydrocarbons (PAHs) in salt marsh plants Spartina alterniflora grown in contaminated sediments

Polycyclic aromatic hydrocarbon (PAH) concentrations were measured in Spartina alterniflora plants grown in pots of contaminated sediment, plants grown in native sediment at a marsh contaminated with up to 900 microg/g total PAHs, and from plants grown in uncontaminated control sediment. The roots and leaves of the plants were separated, cleaned, and analyzed for PAHs. PAH compounds were detected at up to 43 microg/g dry weight in the root tissue of plants grown in pots of contaminated soil. PAH compounds were detected at up to 0.2 microg/g in the leaves of plants grown in pots of contaminated soil. Concentrations less than 0.004 microg/g were detected in the leaves of plants grown at a reference site. Root concentration factor (RCF) values ranged from 0.009 to 0.97 in the potted plants, and from 0.004 to 0.31 at the contaminated marsh site. Stem concentration factor (SCF) values ranged from 0.00004 to 0.03 in the potted plants and 0.0002 to 0.04 at the contaminated marsh. No correlation was found between the RCF value and PAH compound or chemical properties such as logKOW. SCF values were higher for the lighter PAHs in the potted plants, but not in the plants collected from the contaminated marsh. PAH concentrations in the roots of the potted plants are strongly correlated with soil concentrations, but there is less correlation for the roots grown in natural sediments. Additional plants were grown directly in PAH-contaminated water and analyzed for alkylated PAH homologs. No difference was found in leaf PAH concentrations between plants grown in contaminated water and control plants.     

60Co accumulation from sediment and planktonic algae by midge larvae (Chironomus luridus)

This paper reports the results of several experiments carried out to evaluate uptake and retention by a limicolous midge larva of 60Co retained in sediment, either adsorbed on mineral particles or bound to planktonic algae. In order to determine their relative contributions in radionuclide accumulation, the different vectors (water, algae and sediment) were first labelled individually and then simultaneously. 60Co accumulation from water and from algae results in a maximum concentration factor of 30 and in a mean trophic transfer factor of 4.5 x 10(-3). The level of contamination of midge larvae from sediment is markedly influenced by the presence of endogenous organic matter. Thus the radionuclide transfer factor is about twice as high for larvae placed in labelled raw sediment than for larvae placed in labelled incinerated sediment, in the presence as in the absence of contaminated planktonic algae. Irrespective of the contamination conditions, 60Co depuration from midge larvae is a very rapid phenomenon that corresponds, in all cases, to a radionuclide half-life of only a few days.     

颗粒物吸附乐果的动力学特征

研究了乐果在颗粒物表面上吸附的动力学特征,观察了颗粒物的性质对吸附行为的影响.结果表明,乐果在3种颗粒物上的吸附过程均符合一级动力学规律,其相关系数在0.986 2～0.990 5,达到极显著水平.颗粒物的性质与吸附量相关分析发现,不同颗粒物对乐果的吸附程度是由颗粒物的有机质、粘粒、阳离子交换容量(CEC)和pH等理化特征综合作用的结果.pH对吸附行为影响的实验结果指出,随着体系的pH逐渐增大,颗粒物对乐果的吸附能力增强.     

黄河兰州段悬移质泥沙对氨氮的吸附特性

实验研究了黄河兰州段不同粒径的悬浮泥沙对氨氮的吸附行为,拟阐释黄河兰州段水质自净的机制。通过分析探讨了含沙量、氨氮初始浓度、泥沙粒径和化学成分对氨氮吸附过程的影响。结果表明,准二级动力学方程和Langmuir模型能够较好地描述黄河兰州段不同粒径泥沙的吸附动力学和等温吸附过程(R20.9);含沙量对泥沙吸附氨氮作用具有显著影响,且氨氮吸附量和平衡时间与含沙量呈明显负相关性;氨氮初始浓度与氨氮吸附量及平衡时间呈正相关性;同时,泥沙颗粒越细,吸附氨氮的能力越强,吸附容量越大,反应的自发程度越高。此外,泥沙有机质、Fe2O3、Al2O3和MgO的含量随粒径减小而增大,它们对单位质量泥沙最大吸附量(Sm)具有正效应。泥沙的吸附在黄河兰州段水质自净过程中起着一定的促进作用。