‘Emulsion locks’ for the containment of hydrocarbons during surfactant flushing

Reversible double water in oil in water (W/O/W) emulsions were developed to contain subsurface hydrocarbon spills during their remediation using surfactant flushing. Double emulsions were prepared by emulsifying CaCl₂ solutions in canola oil, and subsequently by emulsifying the W/O emulsions in aqueous sodium alginate solutions. The formation of double emulsions was confirmed with confocal and optical microscopy. The double emulsions reversed and gelled when mixed with the surfactants sodium dodecyl sulfate (SDS) and cocamidopropyl betaine (CPB). Gels can act as ‘emulsion locks’ to prevent spreading of the hydrocarbon plume from the areas treated with surfactant flushing, as shown in sand column tests. Shear rheology was used to quantify the viscoelastic moduli increase (gelation) upon mixing the double emulsion with SDS and CPB. SDS was more effective than CPB in gelling the double emulsions. CPB and SDS could adsorb at the interface between water and model hydrocarbons (toluene and motor oil), lowering the interfacial tension and rigidifying the interface (as shown with a Langmuir trough). Bottle tests and optical microscopy showed that SDS and CPB produced W/O and O/W emulsions, with either toluene or motor oil and water. The emulsification of motor oil and toluene in water with SDS and CPB facilitated their flow through sand columns and their recovery. Toluene recovery from sand columns was quantitated using Gas-Chromatography Mass-Spectroscopy (GC-MS). The data show that SDS and CPB can be used both for surfactant flushing and to trigger the gelation of ‘emulsion locks’. Ethanol also gelled the emulsions at 100 mL/L.     

Olive oil mill wastewater for soil nitrogen and carbon conservation

In this work the application of two levels of N fertilizer (NH₄NO₃) dissolved in water or olive oil mill wastewater (OOMW) diluted 10 or 20 times in water, has been studied in relation to the properties of two soils (Loam and Silt-Clay-Loam). Also, the effect of irrigation water bubbled with CO₂ (Dissolved Inorganic Carbon, DIC) was studied. Nitrate N, ammonium N, total N, organic C (OC), and CaCO₃ contents were determined in the soil as well as pH, electrical conductivity (EC), oxidation–reduction potential (ORP), and absorbance at 250 and 360 nm.     

电动力学修复铜污染土壤的研究

采用电动力学方法修复重金属污染土壤。研究中采用高岭土模拟铜污染土壤,电化学装置的电压强度为0.5 V/cm,通过在阴阳极室加入不同的缓冲液来确定铜的迁移效果。结果表明在阴极室加入乙酸作为缓冲液可以有效提高铜的迁移效果,在阳极加入柠檬酸能够有效的与铜形成络合物达到更好的迁移效果。     

土壤镉污染修复方法及生物修复研究进展

土壤镉污染主要由人为活动引起,镉在土壤环境体系中存在复杂多变的形态,文章介绍了土壤镉污染对生物体的危害性及其修复方法,综述了生物修复技术处理镉污染土壤的研究进展,并提出了展望。     

Removal of Cr(VI) from simulative contaminated groundwater by iron metal

The Cr(VI) removal from simulative contaminated groundwater using zero-valent iron (Fe⁰) filings, Fe⁰ powder and nanoscale Fe⁰ in batch experimental mode was studied. Cr(VI) is a primary pollutant of some soils and groundwater. Zero-valent iron, an important natural reductant, could transform Cr(VI) to Cr(III) which is much less toxic and immobile. The Cr(VI) removal percentage was 87% at a metal to solution ratio of 6 g l⁻¹ for commercial iron powder (200 mesh) in 120 min, and 100% Cr(VI) was removed when the metal to solution ratio was 10 g l⁻¹. The results demonstrates that the Cr(VI) removal percentage was affected apparently by pH, the amount of Fe powder and the reaction temperature. The Cr(VI) removal percentage with nanoscale Fe⁰ was much higher than those with Fe⁰ filings or Fe⁰ powder at the same reaction time. Electrochemical analysis of the reaction process led to the conclusion that the Cr(VI) trended to form Cr(III) hydroxide under the reaction conditions. The kinetics analysis showed that Cr(VI) reduction by Fe⁰ could be described as a pseudo-first-order kinetics model.     

A decision framework for possible remediation of contaminated sediments in the River Kymijoki, Finland

Background, aim, and scope  The paper describes the spatial contamination of the River Kymijoki, South-Eastern Finland, and the coastal region of the Gulf of Finland with PCDD/Fs and mercury. The findings of ecotoxicologial and human health studies are also reported, including environmental and human risk assessments. Sediments from the River Kymijoki, draining into the Gulf of Finland, have been heavily polluted by the pulp and paper industry and by chemical industries. A wood preservative, known as Ky-5, was manufactured in the upper reaches of the river between 1940 and 1984 causing severe pollution of river sediments with polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). Moreover, the sediments have been polluted with mercury (Hg) from chlor-alkali production and the use of Hg as a slimicide in pulp and paper manufacturing. Materials and methods  An extensive sediment survey was conducted as well as sediment transport modeling, toxicity screening of sediment invertebrates, and a survey of contaminant bioaccumulation in invertebrates and fish. Studies on human exposure to PCDD/Fs and the possible effects on hypermineralization of teeth as well as an epidemiological study to reveal increased cancer risk were also conducted. An assessment of the ecological and human health risks with a null hypothesis (no remediation) was undertaken. Results  The sediment survey revealed severe contamination of river and coastal sediments with PCDD/Fs and Hg. The total volume of contaminated sediments was estimated to reach 5 × 10⁶ m³ and hot spots with extremely high concentrations (max 292,000 ng g⁻¹ or 1,060 ng I-TEQ g⁻¹ d.w.) were located immediately downstream from the pollution source (approximately 90,000 m³). Sediment contamination was accompanied by changes in benthic assemblages, but direct effects were masked by many factors. The fish showed only slightly elevated PCDD/F levels in muscle, but orders of magnitude higher in the liver compared with reference freshwater sites and the Baltic Sea. The concentrations in human fat did not reveal high human exposure in the Kymijoki area in general and was lower than in sea fishermen. The relative risk for total cancer among farmers was marginally higher (RR = 1.13) among those living close to the river, compared with farmers living further away, and the possibility of increased cancer risk cannot be ruled out. A conservative risk assessment revealed that the present probability of exceeding the WHO upper exposure limit of 4 pg WHO-TEQ kg⁻¹ d⁻¹ for PCDD/Fs and DL-PCBs was 6%. The probability of exceeding the WHO limit value of 0.23 μg kg⁻¹ d⁻¹ for methyl mercury was estimated to be notably higher at 62%. Based on these studies and the estimated risks connected with different remediation techniques a general remediation plan with cost benefit analysis was generated for several sub-regions in the river. Dredging, on-site treatment, and a close disposal of the most contaminated sediments (90,000 m³) was suggested as the first phase of the remediation. The decision regarding the start of remediation will be made during autumn 2008. Conclusions  The sediments in the River Kymijoki are heavily polluted with PCDD/Fs and mercury from earlier chlorophenol, chlor-alkali, and pulp and paper manufacturing. A continuous transport of contaminants is taking place to the Gulf of Finland in the Baltic Sea. The highly increased PCDD/F and Hg levels in river sediments pose an ecotoxicological risk to benthic fauna, to fish-eating predators and probably to human health. The risks posed by mercury exceed those from PCDD/Fs and need to be evaluated for (former) chlor-alkali sites and other mercury releasing industries as one basis for remediation decision making. Recommendations and perspectives  The studies form the basis of a risk management strategy and a plan for possible remediation of contaminated sediments currently under consideration in the Southeast Finland Regional Environment Centre. It is recommended that a detailed restoration plan for the most seriously contaminated areas should be undertaken. Based on current knowledge, the restoration of the whole river is not feasible, considering the current risk caused by the contaminated sediment in the river and the costs of an extensive restoration project. The experiences gained in the present case should be utilized in the evaluation of PCDD/F- and mercury-contaminated sites in other countries. The case demonstrates that the historic reservoirs are of contemporary relevance and should be addressed, e.g., in the national implementation plans of the Stockholm Convention. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Effect of soil texture on surfactant-based remediation of hydrophobic organic-contaminated soil

Surfactants may be used in remediation of subsoil and aquifer contaminated with hydrophobic compounds. The objectives of this study were to examine the effect of soil texture on hydrophobic organic contaminant (HOC; toluene, or 1,2,4-trichlorobenzene [TCB]) removal from six soils and to evaluate the optimal composition of soil texture for maximum HOC removal using aqueous surfactant solution. Selected surfactants were 4% (vol/vol) sodium diphenyl oxide disulfonate (DOSL) and 4% (wt/vol) sodium lauryl sulfate (LS). Toluene and TCB were selected as the lighter-than-water nonaqueous phase liquid (LNAPL) and denser-than-water nonaqueous phase liquid (DNAPL) model substances, respectively. Soil types used for this study were Ottawa sand and five Iowa soils (Fruitfield, Keomah, Crippin, Webster, and Galvar). The greatest recovery of toluene and TCB in batch tests was 73% and 84%, respectively, which was obtained with DOSL surfactant in Ottawa sand. The toluene removal of 95% in column tests has been achieved in the Ottawa sand and three Iowa soils (Fruitfield, Keomah, Crippin) with DOSL after effluent volume of 3750 ml (about 32 pore volume) passed. TCB removal of 98% in column tests has been achieved in Ottawa sand and three Iowa soils (Fruitfield, Keomah, Crippin) with DOSL after effluent volume of 2500 ml (about 21 pore volume) passed. These results were related with soil texture (clay content 30%), clay mineralogy (kaolinite and smectite), as a function of transported pore volume.     

Public and occupational risks of the Nevada (USA) Test Site

The Nevada Test Site (NTS), north of Las Vegas, was the scene of hundreds of nuclear weapons tests over four decades, both above- and belowground. There is considerable interest, both in neighboring communities and elsewhere, in the risks it poses. Overall, the greatest risks are nonradioactive in origin, with occupational risks to employees and accident risks in transporting low-level nuclear wastes to the NTS from other Department of Energy (DOE) sites ranking highest. For radiation risks, that to workers handling radioactive materials is much higher than that to the surrounding population, either present or future. Overall, annual risks are small, with all fatalities approximately 0.008% of total Nevada deaths. At the NTS, the government spends about 5000 times more on radiation as opposed to nonradiation deaths. This suggests that at least some resources may be misallocated towards cleanup of public risks and that the occupational risk of cleanup may be much higher than the public risk. Thus risk may be multiplied by well-meaning programs.     

In situ removal of copper from sediments by a galvanic cell

This study dealt with in situ removal of copper from sediments through an electrokinetic (EK) process driven by a galvanic cell. Iron (Fe) and carbon (C) were placed separately and connected with a conductive wire. Polluted sediments were put between them and water was filled above the sediments. The galvanic cell was thus formed due to the different electrode potentials of Fe and C. The cell could remove the pollutants in the sediments by electromigration and/or electroosmosis. Results showed that a weak voltage less than 1V was formed by the galvanic cell. The voltage decreased with the increase of time. A slight increase of sediment pH from the anode (Fe) to the cathode (C) was observed. The presence of supernatant water inhibited the variation of sediment pH because H(+) and OH(-) could diffuse into the water. The removal of copper was affected by the sediment pH and the distribution of electrolyte in sediment and supernatant water. Lower pH led to higher removal efficiency. More electrolyte in the sediment and/or less electrolyte in the supernatant water favored the removal of copper. The major removal mechanism was proposed on the basis of the desorption of copper from sediment to pore solution and the subsequent electromigration of copper from the anode to the cathode. The diffusion of copper from sediment to supernatant water was negligible.     

Sorption of phenanthrene by dissolved organic matter and its complex with aluminum oxide nanoparticles

Intent of this study was to explore the potential application of polymerin, the polymeric, dissolved organic matter fraction from olive oil wastewaters, in technologies aimed at remediating hydrophobic organic compounds (HOCs) point-source pollution. Phenanthrene binding with polymerin was investigated. Moreover, the effect of addition of micro and nanoscale aluminum oxides (Al₂O₃) was studied, as well as sorption of polymerin on the oxides. Phenanthrene binding capacity by polymerin was notably higher than the sorption capacities for both types of Al₂O₃ particles. Polymerin sorption on nanoparticles was nearly 100 times higher than microparticles. In a three-phase system, using microparticles, higher phenanthrene sorption was found by adding into water polymerin, oxides and phenanthrene simultaneously. In contrast, using nanoparticles, a considerable enhancement of phenanthrene sorption was shown by adding phenanthrene to a pre-formed and dried polymerin-oxide complex. These findings support the application of polymerin, especially associated with Al₂O₃ nanoparticles, in remediation of water contaminated with HOCs. This work highlights the significant role of nanoparticles.