Use of oil shale ash in road construction: results of follow-up environmental monitoring.

Oil shale ash (OSA) was used for road construction in a pristine swamp area in East-Estonia during 2013-2014. OSA was used as a binder both in mass stabilization of soft peat soil and in the upper layer. Use of OSA in civil engineering always raises questions about the environmental safety of such activities. Post-construction environmental monitoring of the pilot section was carried out in 2014 and 2015. The monitoring program involved surface water and soil sampling campaigns. Samples were analyzed for selected constituents and parameters of environmental concern. The paper gives data for assessing the environmental impact and evaluation of potential risks associated with construction of roads using OSA. Leaching of hazardous compounds from the pilot section to surrounding aqueous environment was not observed during the monitoring program. Still, the road construction affected the concentration of sulfates in surrounding surface water. Also, the water-soluble content of barium in surface water correlated significantly with the concentrations of chloride and sulfate ion and electric conductivity of the surface water. Therefore, it is recommended to monitor the electric conductivity, concentrations of sulfates, chlorides, and barium in nearby surface water when OSA is used in road construction.

Leaching of PAHs from agricultural soils treated with oil shale combustion ash: an experimental study.

The present study focuses on the fate of polycyclic aromatic hydrocarbons (PAHs) in soils amended with oil shale ash (OSA). Leachability studies to assess the release of PAHs to the environment are essential before the application of OSA in agriculture. A quantitative estimation of the leaching of PAHs from two types of soil and two types of OSA was undertaken in this study. Two leaching approaches were chosen: (1) a traditional one step leaching scheme and (2) a leaching scheme with pretreatment, i.e.., incubation of the material in wet conditions imitating the field conditions, followed by a traditional leaching procedure keeping the total amount of water constant. The total amount of PAHs leached from soil/OSA mixtures was in the range of 15 to 48 µg/kg. The amount of total PAHs leached was higher for the incubation method, compared to the traditional leaching method, particularly for Podzolic Gleysols soil. This suggests that for the incubation method, the content of organic matter and clay minerals of the soil influence the fate of PAHs more strongly compared to the traditional leaching scheme. The amount of PAHs leached from OSA samples is higher than from soil/OSA mixtures, which suggests soils to inhibit the release of PAHs. Calculated amount of PAHs from experimental soil and OSA leaching experiments differed considerably from real values. Thus, it is not possible to estimate the amount of PAHs leached from soil/OSA mixtures based on the knowledge of the amount of PAHs leached from soil and OSA samples separately.

PAHs in leachates from thermal power plant wastes and ash-based construction materials.

The focus of the current study is to characterise the leaching behaviour of polycyclic aromatic hydrocarbons (PAHs) from oil shale ashes (OSAs) of pulverised firing (PF) and circulating fluidised-bed (CFB) boilers from Estonian Thermal Power Plant (Estonia) as well as from mortars and concrete based on OSAs. The target substances were 16 PAHs from the EPA priority pollutant list. OSA samples and OSA-based mortars were tested for leaching, according to European standard EN 12457-2 (2002). European standard CEN/TC 15862(2012) for monolithic matter was used for OSA-based concrete. Water extracts were analysed by GC-MS for the concentration of PAHs. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene were detected. Still, the release of PAHs was below the threshold limit value for inert waste. The amount of the finest fraction (particle size <0.045 mm), the content of the Al-Si glass phase and the surface characteristics were the main factors, which could affect the accessibility of PAHs for leaching. The mobility of PAHs from OSA of CFB and PF boilers was 20.2 and 9.9%, respectively. Hardening of OSA-based materials did not lead to the immobilisation of soluble PAHs. Release of PAHs from the monolith samples did not exceed 0.5 µg/m(2). In terms of leaching of PAHs, OSA is safe to be used for construction purposes.

Leaching of polycyclic aromatic hydrocarbons from oil shale processing waste deposit: a long-term field study.

The leaching behavior of selected polycyclic aromatic hydrocarbons (PAHs) from an oil shale processing waste deposit was monitored during 2005-2009. Samples were collected from the deposit using a special device for leachate sampling at field conditions without disturbance of the upper layers. Contents of 16 priority PAHs in leachate samples collected from aged and fresh parts of the deposit were determined by GC-MS. The sum of the detected PAHs in leachates varied significantly throughout the study period: 19-315 µg/l from aged spent shale, and 36-151 µg/l from fresh spent shale. Among the studied PAHs the low-molecular weight compounds phenanthrene, naphthalene, acenaphthylene, and anthracene predominated. Among the high-molecular weight PAHs benzo[a]anthracene and pyrene leached in the highest concentrations. A spent shale deposit is a source of PAHs that could infiltrate into the surrounding environment for a long period of time.

The use of bioassays for the risk assessment of toxic leachates: an experimental study.

Solid wastes from the oil-shale industry produce leachates containing toxic compounds such as heavy metals and persistent polycyclic aromatic hydrocarbons (PAH). The hazard to the environment represented by waste leachates depends not only on their chemical composition, but also on the mobility and bioavailability of toxic contaminants in soils. We evaluated the applicability of bioassays for toxicity assessment of the bioavailable fraction of heavy metals and PAH in soils, in experiments with samples of four different soil types (Rendzina, Brown pseudopodzolic, Typical brown, Sodpodzolic), the pH of which ranged from 6.2 to 7.2. The toxicity of the bioavailable fraction of the soil contaminants was assessed with the dehydrogenase enzyme activity assay, and with a Toxkit microbiotest with the crustacean, Thamnocephalus platyurus, after treatment of the soil samples with an artificial solution containing chromium (III), lead (II), copper (II), cadmium (II) and pyrene. The test results confirm those of earlier experiments, which characterised the sorption potential of investigated soils for the same compounds. Both tests turned out to be sufficiently sensitive, and hence can be recommended as effective and useful tools for the assessment of the bioavailable fraction of soil contaminants.

The role of laboratory and field leaching tests in hazard identification for solid materials.

The use of various in vitro toxicity assays for testing environmental solid samples is dependent on the availability of reliable methods for the sampling and pretreatment of the material. This study focuses on the evaluation of leaching behaviour as a first step in the context of the toxicity testing of solid environmental matter. Spent shale, from oil shale retorting, was chosen as a suitable example of deposited solid waste material. For the generation of leachate in the laboratory setting, a standard two-stage batch-leaching test was applied to the samples of technogenic waste. In the field, a new type of lysimeter, which does not disturb the surface, was used for in situ leachate collection. The chemical composition of water extracts was found to be different under field conditions, as compared with the laboratory experiments. Thus, the hazard identification of a solid technogenic waste by in vitro toxicological tests applied to laboratory leachates would not be the best solution. The content of hazardous ingredients could be underestimated if only laboratory tests are used. For risk assessment concerned with solid waste materials, the generation of leachate by using field lysimeters is recommended.

Effect of heavy metals and PAH on soil assessed via dehydrogenase assay.

Dehydrogenase enzyme activity (DHA) assay method using resazurin was accommodated for measuring of toxicity of compound contaminants on uncharacterized microbial communities present in any given soil. The method was used to compare the toxic effect of heavy metal and polycyclic aromatic hydrocarbon (PAH) contaminant mixture (Cr, Pb, Cu, Cd, Pyrene) on four typical Estonian soils covering a range of compositions. The method proved to be useable on all soils; the sensitivity of soil microbiology to toxic effect of contaminants was found to have a negative correlation with Ca and organic matter (OM) content and a positive correlation with amorphous phase content of soils.