Effects of dissolved organic phase composition and salinity on the engineered sulfate application in a flow-through system.

Engineered sulfate application has been proposed as an effective remedy to enhance the rate-limited biodegradation of petroleum-hydrocarbon-contaminated subsurface environments, but the effects of dissolved organic phase composition and salinity on the efficiency of this method are unknown. A series of flow-through experiments were conducted for 150 days and dissolved benzene, toluene, naphthalene, and 1-methylnaphthalene were injected under sulfate-reducing and three different salinity conditions for 80 pore volumes. Then, polycyclic aromatic hydrocarbons (PAHs) were omitted from the influent solution and just dissolved benzene and toluene were injected to investigate the influence of dissolved phase composition on treatment efficiency. A stronger sorption capacity for PAHs was observed and the retardation of the injected organic compounds followed the order of benzene < toluene < naphthalene < 1-methylnaphthalene. Mass balance analyses indicated that 50 and 15% of toluene and 1-methlynaphtalene were degraded, respectively. Around 5% of the injected naphthalene degraded after injecting > 60 PVs influent solution, and benzene slightly degraded following the removal of PAH compounds. The results showed substrate interactions and composition can result in rate-limited and insufficient biodegradation. Similar reducing conditions and organic utilization were observed for different salinity conditions in the presence of the multi-component dissolved organic phase. This was attributed to the dominant microbial community involved in toluene degradation that exerted catabolic repression on the simultaneous utilization of other organic compounds and were not susceptible to changes in salinity.

Sorption of benzene and naphthalene on (semi)-arid coastal soil as a function of salinity and temperature.

Considerable activities from the oil and natural gas sector have risen some concerns about the pollution of soil and groundwater by petroleum hydrocarbons (PHCs) in (semi)-arid coastal regions. The understanding of the fate and transport of PHCs in these regions is therefore necessary to develop strategies for remediation. To quantify the sorption rates of PHCs in (semi)-arid coastal soil environments, we conducted a series of controlled-laboratory batch experiments under variable temperature and salinity conditions. The soil samples were collected from the eastern coast of Qatar which is near the two largest off-shore oil and natural gas fields of the country (North Gas and Al-Shaheen Oil Fields), and the volatile benzene and naphthalene were used as PHCs. The characterization of soil samples showed sand classification with the texture class of sabkha and saline beach sandy soils with calcite as potential dominant mineral. The concentrations of dissolved chloride and sodium were found to be high (> 400 mg L-1) with a chloride-to­sodium ratio of about 1.7. The results of sorption experiments showed that the rates of naphthalene sorption were more than for benzene, where the initial aqueous concentrations of benzene and naphthalene were reduced at equilibrium due to sorption by about 14-25% and 65-79%, respectively. This difference was attributed mainly to the organic carbon-water partitioning coefficient which is higher for naphthalene. The sorption rate experiments showed that sorption was stronger for benzene under higher salinity and lower temperature conditions. The sorption of naphthalene was not affected by the change in salinity but increased by 18% when the temperature decreased from 35 to 5 °C. A sorption kinetic model was also applied to define the sorption behavior of benzene and naphthalene for the coastal soil collected in Qatar and the best fits were achieved with the Langmuir sorption isotherm.

Altered transport of lindane caused by the retention of natural particles in saturated porous media.

Attachment and straining of colloidal particles in porous media result in their reversible and irreversible retention. The retained particles may either increase the retention of hydrophobic pollutants by sorption onto the particles, or enhance pollutant transport when particles, loaded with the pollutants, are remobilized. The present study examines the effects of retained particles on the transport of the hydrophobic pesticide lindane (gamma-hexachlorocyclohexane) in saturated porous media. The lignite particles used have median diameters of about 3 µm, 1 µm, 0.8 µm, and 0.2 µm, respectively. Laboratory column experiments were analyzed by numerical modeling in order to identify and understand the processes involved in the transport of the particles and of lindane. Four scenarios were considered in which the solution containing lindane is injected either during or after the elution of the particles. The results show that lignite particles retained in a sandy porous medium alter the transport of the invading lindane. Particle retention was high in all scenarios and increased with increasing particle size. Remobilization of particles occurred due to a change in solution chemistry, and continuous particle detachment was observed over time. Numerical modeling of particle transport suggests that both reversible attachment and irreversible straining affected the transport of the particles. Lindane was retarded in all scenarios due to the strong particle retention in conjunction with the sorption of lindane onto the sand and onto retained particles, and the limited number of mobile particles carrying lindane. Moreover, it was found that intra-particle diffusion limited adsorption/desorption of lindane onto/from both limestone fragments of the sand and lignite particles. We assume that retention of lindane is reversible even though lindane recovery was incomplete over the duration of the experiments. The analysis of the effluent concentration suggests that retained particles loaded with lindane may become a secondary source of lindane. Models describing the transport of lindane fitted the experimental data very well and indicated the specific contribution of retained particles to the retardation of lindane. Since the properties of lignite also known as brown coal are similar to those of biochar, the results of the present study could be extended to the potential effects of biochar on lindane and other contaminants in soils, which would include both their retention and their enhanced transport. However, while the transport mechanisms of lindane are similar in water-unsaturated soils and saturated porous media considered here, the behavior of particles is more complex, requiring additional studies.

Particle-facilitated transport of lindane in water-saturated tropical lateritic porous media.

The persistent insecticide lindane [(1α,2α,3ß,4α,5α,6ß)-1,2,3,4,5,6-hexachlorocyclohexane] is still in use in many tropical countries and remains a threat to soil and water quality. We studied the sorption and transport of lindane onto and through lateritic soils in both the absence and presence of lignite particles, onto which lindane may preferably sorb. We determined a linear distribution coefficient of lindane onto the soil matrix of 3.38 ± 0.16 L kg. Soil particles were not released from the porous medium on changing ionic strength, and also transport of lindane was not affected by changes in ionic strength. We fitted coupled transport models for lindane and the particles to the data, revealing that: (i) sorption kinetics of lindane onto the matrix is described best by intraparticle diffusion; (ii) 20% of the total porosity of the lateritic sample is intraparticle porosity; and (iii) only lignite particles with a median diameter <0.45 µm were not retained in the porous medium and thus facilitated the transport of lindane. We conclude that although lindane and similar pollutants may sorb on tropical lateritic porous media, their transport may be facilitated by particles with high organic-C content or dissolved organic C (DOC). This may be of relevance in farmlands and swamp groundwater systems where DOC, produced by leaching or slow biodegradation of surface organic matter, could cause rapid groundwater contamination by sorbing pollutants. Moreover, the results of this study can help to understand nanoparticle behavior in lateritic soils as the size of particles that facilitate lindane transport approaches the nanoparticle size range.

Effect of natural particles on the transport of lindane in saturated porous media: laboratory experiments and model-based analysis.

Colloidal particles can act as carriers for adsorbing pollutants, such as hydrophobic organic pollutants, and enhance their mobility in the subsurface. In this study, we investigate the influence of colloidal particles on the transport of pesticides through saturated porous media by column experiments. We also investigate the effect of particle size on this transport. The model pesticide is lindane (gamma-hexachlorocyclohexane), a representative hydrophobic insecticide which has been banned in 2009 but is still used in many developing countries. The breakthrough curves are analyzed with the help of numerical modeling, in which we examine the minimum model complexity needed to simulate such transport. The transport of lindane without particles can be described by advective-dispersive transport coupled to linear three-site sorption, one site being in local equilibrium and the others undergoing first-order kinetic sorption. In the presence of mobile particles, the total concentration of mobile lindane is increased, that is, lindane is transported not only in aqueous solution but also sorbed onto the smallest, mobile particles. The models developed to simulate separate and associated transport of lindane and the particles reproduced the measurements very well and showed that the adsorption/desorption of lindane to the particles could be expressed by a common first-order rate law, regardless whether the particles are mobile, attached, or strained.