Availability and leaching of polycyclic aromatic hydrocarbons: Controlling processes and comparison of testing methods

We have studied the availability and leaching of polycyclic aromatic hydrocarbons (PAHs) from two contaminated materials, a tar-containing asphalt granulate (Sigma16 US-EPA PAHs 3412mg/kg) and gasworks soil (SigmaPAHs 900mg/kg), by comparing results from three typical types of leaching tests: a column, sequential batch, and two different availability tests. The sequential batch test was found to largely resemble the column test. However, the leaching of particularly the larger PAHs (>5 aromatic rings) was found to be enhanced in the batch test by up to an order of magnitude, probably due to their association with large DOC (dissolved organic carbon) molecules generated by the vigorous mixing. The release of PAHs in the two availability tests, in which the leaching is facilitated by either a high concentration of DOC or Tenax resin, was similar, although the latter test was easier to perform and yielded more repeatable results. The availability was much higher than the amount leached in the column and sequential batch tests. However, biodegradation had apparently occurred in the column test and the total amount of PAHs released by either leaching or biodegradation, 9% and 26% for asphalt granulate and gasworks soil, respectively, did equal the amount leached in the availability tests. Therefore, the availability was found to provide a relevant measure of the PAH fraction that can be released from the solid phase. These results stress the importance of using the available instead of the total amount of contaminant in the risk analysis of solid materials in utilization or disposal.     

Comparison of percolation to batch and sequential leaching tests: Theory and data

Leaching tests are becoming more relevant in assessing solid waste material, particularly with respect to groundwater risks. In the field, water infiltration is the dominant leaching mechanism, which is simulated in the lab with batch and column tests. In this study, we compared percolation, through analytical solutions of the advection–dispersion equation, to laboratory batch and sequential leaching tests. The analytical solutions are supported with comprehensive data from various field and laboratory leaching of different solutes from waste materials and soils collected in long-term joint research projects funded by the German Federal Ministry for Education and Research and the Federal Environment Agency. The comparison of theory and data is facilitated if concentrations and cumulative release are plotted versus the liquid–solid ratios (LS). Both theory and data indicate that leaching behaviour is independent of duration and physical dimensions of the leaching tests. This holds even if field lysimeters are compared to laboratory columns of different size, different flow velocities as well as different contact times. In general, laboratory batch tests over predict effluent concentrations (for LS < K_d). Leaching of solutes from solid samples of certain materials (e.g. chloride from incineration ashes or sulphate from demolition waste) in column and lysimeter tests compares very well and agrees with the analytical solutions. Overall, reproducibility and agreement with theory of column tests are better than batch tests, presumably because the latter are prone to artefacts (e.g. in liquid–solid separation steps). Theory and data fit surprisingly well, despite the fact that the theory is based on the local equilibrium assumption; non-linear sorption and chemical reactions in the solid waste materials are not considered.     

Characterisation of major component leaching and buffering capacity of RDF incineration and gasification bottom ash in relation to reuse or disposal scenarios

Thermal treatment of refuse derived fuel (RDF) in waste-to-energy (WtE) plants is considered a promising solution to reduce waste volumes for disposal, while improving material and energy recovery from waste. Incineration is commonly applied for the energetic valorisation of RDF, although RDF gasification has also gained acceptance in recent years. In this study we focused on the environmental properties of bottom ash (BA) from an RDF incineration (RDF-I, operating temperature 850-1000 °C) and a RDF gasification plant (RDF-G, operating temperature 1200-1400 °C), by evaluating the total composition, mineralogy, buffering capacity, leaching behaviour (both at the material’s own pH and as a function of pH) of both types of slag. In addition, buffering capacity results and pH-dependence leaching concentrations of major components obtained for both types of BA were analysed by geochemical modelling. Experimental results showed that the total content of major components for the two types of BA was fairly similar and possibly related to the characteristics of the RDF feedstock. However, significant differences in the contents of trace metals and salts were observed for the two BA samples as a result of the different operating conditions (i.e. temperature) adopted by the two RDF thermal treatment plants. Mineralogy analysis showed in fact that the RDF-I slag consisted of an assemblage of several crystalline phases while the RDF-G slag was mainly made up by amorphous glassy phases. The leached concentrations of major components (e.g. Ca, Si) at the natural pH of each type of slag did not reflect their total contents as a result of the partial solubility of the minerals in which these components were chemically bound. In addition, comparison of total contents with leached concentrations of minor elements (e.g. Pb, Cu) showed no obvious relationship for the two types of BA. According to the compliance leaching test results, the RDF-G BA would meet the limits of the Italian legislation for reuse and the European acceptance criteria for inert waste landfilling. RDF-I BA instead would meet the European acceptance criteria for non hazardous waste landfilling. A new geochemical modelling approach was followed in order to predict the leaching behaviour of major components and the pH buffering capacity of the two types of slags on the basis of independent mineralogical information obtained by XRD analysis and the bulk composition of the slag. It was found that the combined use of data regarding the mineralogical characterization and the buffering capacity of the slag material can provide an independent estimate of both the identity and the amount of minerals that contribute to the leaching process. This new modelling approach suggests that only a limited amount of the mineral phases that control the pH, buffering capacity and major component leaching from the solid samples is available for leaching, at least on the time scale of the applied standard leaching tests. As such, the presented approach can contribute to gain insights for the identification of the types and amounts of minerals that control the leaching properties and pH buffering capacity of solid residues such as RDF incineration and gasification bottom ash.     

Evaluating two test methods used for characterizing leaching properties

A standard leaching test method (EN 12457-3) was compared with a modified pHstat-column leaching test method with respect to leaching information obtained for aggregates composed of different alkaline solid wastes. In addition to a different experimental set-up, the major dissimilarity between the two test methods was the chemical equilibrium condition, i.e., in the first test the system approaches equilibrium while in the second test the system is far from equilibrium conditions. The leaching trends of sodium, calcium, chloride, sulfate and cadmium were studied. Results showed that these two test methods were comparable in respect to the total amount sodium and sulfate leached. It was also concluded that the two test methods provide different information for the constituents for which dissolution reaction is highly dependent on pH and other experimental conditions, e.g., flow rate. It was found that a batch test can be used in order to investigate the total amount leached, while a modified column-pHstat test generates more detailed results on leaching trends of some constituents.     

Leachability testing of metallic wastes.

The performance of two tests, a batch test and a percolation test for the characterization of waste as suggested in the EU council decision 2003/33/EC was investigated. The tests were carried out on two solid waste streams from a metal recycling industry. The concentrations of heavy metals such as Cu, Zn and Pb were more than one order of magnitude lower than the proposed limit values. Generally, batch test values were equal or higher than percolation test values. With the proposed test procedures both materials could be considered as non-dangerous wastes. The test performance was also investigated using a leachant with higher ionic strength instead of demineralized water as prescribed. The results clearly show a significant increase in the concentration of some heavy metals. Total concentrations of phenolic compounds and polychlorinated biphenyls were less than 1 p.p.m. and 2 p.p.b., respectively. The precision of the batch and the percolation tests were on average 48 and 35%, respectively.     

Leaching of wood ash products aimed for spreading in forest floors--influence of method and L/S ratio

Use of biofuels in the form of logging residues is increasing in the European countries. This intensive forestry, where entire trees are removed from the felling sites, may contribute to a negative nutrient balance in the forest soil. Recycling of ash from the combustion of clean wood fuel, sometimes in combination with limestone or additives/binders, back into the forest soil could maintain the soil nutrient reservoir intact. Before spreading ash, it is important to determine its contents and, particularly, its decomposition pattern using reliable laboratory leaching tests. In this study, mineralogy and the leaching of Na, Ca, K, Mg, Mn, Al, Cu, Fe, P, and Zn from wood ash pellets and granules, produced both from green liquor sludge and fly ash, are examined by XRD and by subjecting these substances to three different laboratory leaching tests: upflow percolation (CEN/TS 14405), batch leaching (SS-EN12457), and a new Swedish leaching test using a magnetic stirrer. Mineral phases such as quartz, ettringite, calcite, gehlenite, and aphtitalite were identified in the ash granules and in the ash/green liquor sludge granules, by means of XRD. Six additional minerals were detected in the granules of ash only, and another six in the ash/green liquor sludge granules. At L/S 2, the batch leaching test resulted in the highest amounts of elements leached and the upflow percolation test the lowest. At L/S 10, both the batch leaching test and the upflow percolation test resulted in high amounts of elements leached. The batch leaching test at L/S 10 complies quite well with the percolation test and could be suitable for ash/green liquor sludge granule evaluation in daily practice. The magnetic stirrer test seems to underestimate the release potential of elements from granules. The batch test is simple to perform, and has the ability to dissolve 70-80% of the elements with the highest mobility from the materials under study.     

Percolation and batch leaching tests to assess release of inorganic pollutants from municipal solid waste incinerator residues

In this study, percolation and batch leaching tests were considered in order to characterize the behaviour of air pollution control (APC) residues produced in a municipal solid waste incinerator (MSWI) as a function of the liquid to solid ratio (L/S). This waste is hazardous, and taking into account their physical and chemical properties, leaching of contaminants into the environment is the main concern. In our work the leaching behaviour of toxic heavy metals (Pb, Zn, Cr, Ni and Cu) and inorganics associated with soluble salts (Na, K, Ca and Cl) was addressed. Although pH of the leaching solution is the most important variable, L/S may also play an important role in leaching processes. In our work, results from column and batch tests were compared in terms of concentration (mg/L) and releasing (mg/kg). The APC residues revealed to be hazardous according to both tests, and both Pb and Cl⁻ far exceeded the regulatory thresholds. The material exhibits high solubility, and when the liquid to solid ratio was high, more than 50% can be solubilised. The patterns of release may be in some cases availability or solubility controlled, and the former was easier to identify. When the results from column and batch experiments were compared by representing the cumulative released amounts (in mg/kg) as a function of L/S, both curves match for Zn, Ni, Cu, K, Na, Cl and Ca, but for Cr and Pb a significant difference was observed. In fact, the column experiments revealed that under percolation conditions it should be expected slow releasing of Pb along time. From this study, it can be concluded that the released amounts obtained in batch experiments for a certain L/S should be considered as the worst case for medium term. Some simple models proposed on the literature and based on local equilibrium assumption showed good fitting to experimental data for soluble species (non-reactive solutes).     

Recycling municipal incinerator fly- and scrubber-ash into fused slag for the substantial replacement of cement in cement-mortars

Fly- and scrubber-ash (weight ratio of approximately 1:3) from municipal solid waste incinerators (MSWI) are a major land-fill disposal problem due to their leaching of heavy metals. We uniformly mixed both types of ash with optimal amounts of waste glass frit, which was then melted into a glassy slag. The glassy slag was then pulverized to a particle size smaller than 38 μm for use as a cement substitute (20–40% of total cement) and blended with sand and cement to produce slag-blended cement-mortar (SCM) specimens. The toxicity characteristics of the leaching procedure tests on the pulverized slag samples revealed that the amount of leached heavy metals was far below regulatory thresholds. The compressive strength of the 28-day cured SCM specimens was comparable to that of ordinary Portland cement mortars, while the compressive strength of specimens cured for 60 or 90 days were 3–11% greater. The observed enhanced strength is achieved by Pozzolanic reaction. Preliminary evaluation shows that the combination of MSWI fly- and scrubber-ash with waste glass yields a cost effective and environmentally friendly cement replacement in cement-mortars.     

Effect of drying on leaching testing of treated municipal solid waste incineration APC-residues

Air-pollution-control (APC) residues from waste incinerators are hazardous waste according to European legislation and must be treated prior to landfilling. Batch and column leaching data determine which type of landfill can receive the treated APC-residues. CEN standards are prescribed for the batch and column leaching test; however, these standards do not specify whether or not the residue samples should be dried prior to the leaching testing. Laboratory tests were performed in parallel (dried/non-dried) on treated APC-residue samples and evaluated with respect to Cr, Cd, Cu, Pb and Zn leaching. The effect of drying of the wet APC-residue samples was particularly dramatic regarding the leaching of Cr. Drying resulted in 10-100 times more Cr leaching in both batch and columns test. Drying also affected the leaching of Cd, Cu and Pb. Initial Cd leaching was up to 100 times higher in column tests with dried APC-residue than in tests with wet residues. The effect of drying appeared to be a combination of decreasing the reduction capacity of the sample (Cr), decreasing pH (Cd, Cu) and in column tests also a wash-out of salts (probably affecting Cd and Pb). If the leaching tests are intended to mimic landfill conditions, the results of this paper suggest that the tests should be done on wet, non-dried residue samples, although this may be less practical than testing dried samples.     

Long-term leaching test of incinerator bottom ash: evaluation of Cu partition

Two types of leaching tests were performed on the bottom ash from municipal solid waste incinerators. A short-term batch test specified by the America Nuclear Society (ANS) and long-term column tests with acetic acid (pH 5.2) as leaching solution were used to evaluate copper leachability. The Cu leaching after the 5-d ANS test is about 1% of the original Cu content of 5300 mg/kg. Upon addition of a stabilizing agent, the Cu leaching quantity is reduced; the extent of reduction depends on the type of chemical used (phosphate, carbonate and sulfide). The 1.6% Na(2)S addition showed negligible Cu leaching, and Na(2)S was, therefore, used in subsequent column tests. The 30-d column test indicates a steady increase of Cu leaching amount with time and reaches about 1.5% of the original Cu content after 30 d. A 180-d column test further increased the Cu leaching to about 5.1% of the original Cu content, whereas no appreciable Cu leaching was found with the addition of 1.6% Na(2)S. A sequential extraction was conducted on the raw ash, ash with the addition of Na(2)S and the residue ash after 30 d of operation to characterize Cu affinity for different solid fractions. The data were used to evaluate the fate of Cu through these interactions.     

Leachate from land disposal of coal fly ash

The results of large-scale lysimeter tests in which two pulverized coal fly ashes (PCFA) have been exposed to natural weather conditions for up to seven years are presented and compared with those of laboratory leaching tests. Laboratory column leaching tests on PCFA show good reproducibility, and comparisons between lysimeter and laboratory leaching results are promising for several salt ions and trace elements in the leachate when expressed in terms of the leachate to solids ratio (L/S). A long-term disposal strategy which takes into account the largely insoluble nature of PCFA is suggested.     

Optimization of sprayed lime amount in the semi-dry scrubbing system of MSWI

This paper reports the characterization of residues collected from air pollution controlling devices (APCDs) at seven large-scale municipal solid wastes (MSW) incineration plants. The amount of lime being sprayed in plants is a function of free CaO content in scrubber residues; a higher free CaO content in scrubber residue causes more leaching of lead. The proper amount of lime in the semi-dry scrubbing system was found to be 5kg/ton of MSW waste. Under these conditions, both the free CaO content and lead leaching became extremely low in scrubber residue.     

Leaching behavior of heavy metals and PAHs from MSWI bottom ash in a long-term static immersing experiment

Bottom ash is the main solid residue (in weight) which is produced by municipal solid waste incineration (MSWI) facilities. This material is composed of a mineral matrix and may be used as secondary raw material for construction purpose. However, for this specific application the leaching behavior of the environmentally relevant elements under field conditions is different from the predicted behavior based on results obtained from the standardized leaching test. Therefore, a 70-day simulative experiment has been carried out in this study to investigate the release of major heavy metals (Cu and Pb) and polycyclic aromatic hydrocarbons (PAHs) from several particle fractions of bottom ash under a static leaching condition, where bottom ash was immersed in water at different initial pH values. Results showed that: (1) the leaching behavior of Cu and Pb was much similar with that depicted by the standardized leaching tests, and fit well with the solubility-controlling mechanism; (2) the sorption mechanism on the neoformed phases may control the solubility of Pb, whereas the dissolved organic carbon (DOC) may play an important role in the solubility of Cu; and (3) the leached PAHs were degraded during the later period of leaching process.     

Evaluation of leaching and extraction procedures for soil and waste

Laboratory leaching tests may be used for source term determination as a basis for risk assessment for soil-groundwater pathways on contaminated sites. In order to evaluate different leaching procedures, batch extraction tests and percolation tests were performed using three reference materials produced from contaminated soil, demolition waste and municipal solid waste incinerator bottom ash. Emphasis was placed on the investigation of the leachability of the heavy metals copper and chromium, polycyclic aromatic hydrocarbons (PAHs) and the anions chloride and sulfate. Significant discrepancies between column experiments and batch/extraction tests were found for the release of PAHs and to a lesser extent for the heavy metals Cu and Cr. Additionally interlaboratory comparisons were conducted based on different leaching tests with the reference materials and evaluated using the criteria of comparability and reproducibility. The best reproducibility was achieved for all investigated substances in column tests. The reproducibility of batch tests was acceptable except for PAHs. The results from the experimental work will help establish standardized and feasible laboratory procedures as fundamental for substance specific risk assessment of contaminated sites.     

Leachability testing of sludge from street gullies.

Sludge from gullies, on two types of streets with different traffic intensity, was investigated using two recommended EU methods for leachability testing of waste: a two-stage batch test and an up-flow percolation test. The main purpose of this investigation was to gain more knowledge about these leaching test methods to be able to make future decisions on the general applicability of the proposed tests. A number of parameters were determined in the sludge as well as in the eluates obtained from the two leaching tests. These include pH, conductivity, dissolved organic carbon and inorganic ions as chloride ions. A number of metals as Cd, Cr, Cu, Hg, Ni and Zn, were determined by inductive coupled plasmamass spectrometry and organic compounds were screened by high performance liquid chromatography-diode array UV detection and gas chromatography-mass spectrometry. It was found that the concentrations of metals and organic compounds in the sludge were several orders of magnitudes higher than the actual eluate concentrations. For all metals the concentrations were well below the proposed limit values for non-hazardous waste included in the Council decision document 2003/33/EC. Generally, concentrations obtained in batch test were equal or higher than from percolation tests. The repeatability of the percolation and the batch test were in average 28 and 17%, respectively.     

Test methods for assessing the biological stability of biodegradable waste

This paper presents some results of investigations for the characterization of waste excavated from closed landfills and of waste sampled during mechanical-biological pretreatment before disposal in landfill. The results reported are those obtained with the tests carried out for the assessment of the biological stability of the waste. Some of the considered tests, such as the ones for the determination of the respiration activity and the biogas production, are well known and have been applied for years; other tests, such as the ones for the determination of BOD5 and COD in leaching test eluate and of the black index, are among the tests considered by the international research community for possible utilization for the evaluation of waste biological stability. Good correlations were found for most of the results obtained, proving the reliability of the test methods used. In particular, the effectiveness of biodegradation during waste pretreatment processes can be easily monitored by measuring the respiration index and/or the BOD5 and COD in leaching test eluate; for the characterization of waste from landfills, the use of respiration index can be recommended. In both cases the COD in leaching test eluate may provide additional useful information especially in the case of low values for the respiration index. Moreover, the black index test may be considered with some limits that will be discussed, providing good results in a simple and cost effective way.     

Assessment of mobility and bioavailability of contaminants in MSW incineration ash with aquatic and terrestrial bioassays

Incineration of municipal solid waste (MSW) is a waste treatment method which can be sustainable in terms of waste volume reduction as well as a source of renewable energy. In the process fly and bottom ash is generated as a waste material. The ash residue may vary greatly in composition depending on the type of waste incinerated and it can contain elevated levels of harmful contaminants such as heavy metals. In this study, the ecotoxicity of a weathered, untreated incineration bottom ash was characterized as defined by the H14 criterion of the EU Waste Framework Directive by means of an elemental analysis, leaching tests followed by a chemical analysis and a combination of aquatic and solid-phase bioassays. The experiments were conducted to assess the mobility and bioavailability of ash contaminants. A combination of aquatic and terrestrial bioassays was used to determine potentially adverse acute effects of exposure to the solid ash and aqueous ash leachates. The results from the study showed that the bottom ash from a municipal waste incineration plant in mid-Sweden contained levels of metals such as Cu, Pb and Zn, which exceeded the Swedish EPA limit values for inert wastes. The chemical analysis of the ash leachates showed high concentrations of particularly Cr. The leachate concentration of Cr exceeded the limit value for L/S 10 leaching for inert wastes. Filtration of leachates prior to analysis may have underestimated the leachability of complex-forming metals such as Cu and Pb. The germination test of solid ash and ash leachates using T. repens showed a higher inhibition of seedling emergence of seeds exposed to the solid ash than the seeds exposed to ash leachates. This indicated a relatively low mobility of toxicants from the solid ash into the leachates, although some metals exceeded the L/S 10 leaching limit values for inert wastes. The Microtox® toxicity test showed only a very low toxic response to the ash leachate exposure, while the D. magna immobility test showed a moderately high toxic effect of the ash leachates. Overall, the results from this study showed an ecotoxic effect of the solid MSW bottom ash and the corresponding ash leachates. The material may therefore pose an environmental risk if used in construction applications. However, as the testing of the solid ash was rather limited and the ash leachate showed an unusually high leaching of Cr, further assessments are required in order to conclusively characterize the bottom ash studied herein as hazardous according to the H14 criterion.     

Characterization of a mineral waste resulting from the melting treatment of air pollution control residues

Air pollution control (APC) residues which are generated by municipal solid waste (MSW) incineration show a high-level of pollution potential. In order to stabilize such APC residues, the French power supply company (EDF) is developing a thermal treatment process which leads to the production of a vitrified material. A structural characterization of the vitrified product was carried out by applying complementary investigation methods: XRD, SEM, Raman spectroscopy, EPMA, and data interpretation methods such as mineralogical analysis and principal component analysis (PCA). The major phase of the material was a solid solution of melilite type composed of five end-members: gehlenite (44%), åkermanite (25%), ferri-gehlenite (5%), sodamelilite (14%) and hardystonite (11%). The minor phases identified were spinels and pyroxenes.An ANC leaching test was performed in order to observe the treatment effect on pollutant release. The natural pH was close to 10, and the major element release was less than in the case of untreated APC. This was a consequence of melilite formation. The effect of pH was fundamental for heavy metals release: lower solubilization occurs at pH 10 than at APC’s natural pH (11–12).     

Evaluation of heavy metal leaching from spent household batteries disposed in municipal solid waste

Batch leaching tests and simulated landfill lysimeter tests were performed to evaluate the contents of heavy metals leached from spent batteries in the municipal solid waste. The toxicity characteristic leaching procedure was utilized to perform the batch leaching tests of 36 spent batteries. Four lysimeters were prepared with battery contents ranging from 0% to 100% by weight for column tests, and the experiments were performed at ambient temperature. The age of all the batteries used in the study ranged from freshly disposed up to approximately 3 years old. The results from the batch tests showed that the type of battery influenced the heavy metal concentrations in the leached solutions. The lysimeter experiment results illustrated that at lower pH levels more metals are leached than at higher pH levels. The increasing amount of batteries disposed in landfills can contribute to the leaching of more metals, especially Mn and Zn, into the environment. These results indicate that the direct disposal of spent household batteries into a MSW landfill can increase the heavy metal contents in the landfill leachate.     

Assessment of the possible reuse of MSW coming from landfill mining of old open dumpsites

The present study addresses the theme of recycling potential of old open dumpsites by using landfill mining. Attention is focused on the possible reuse of the residual finer fraction (<4 mm), which constitutes more than 60% of the total mined material, sampled in the old open dumpsite of Lavello (Southern Italy). We propose a protocol of analysis of the landfill material that links chemical analyses and environmental bioassays. This protocol is used to evaluate the compatibility of the residual matrix for the disposal in temporary storages and the formation of “bio-soils” to be used in geo-environmental applications, such as the construction of barrier layers of landfills, or in environmental remediation activities. Attention is mainly focused on the presence of heavy metals and on the possible interaction with test organisms. Chemical analyses of the residual matrix and leaching tests showed that the concentration of heavy metals is always below the legislation limits. Biological acute tests (with Lepidum sativum, Vicia faba and Lactuca sativa) do not emphasize adverse effects to the growth of the plant species, except the bioassay with V. faba, which showed a dose–response effect. The new developed chronic bioassay test with Spartium junceum showed a good adaptation to stress conditions induced by the presence of the mined landfill material. In conclusion, the conducted experimental activities demonstrated the suitability of the material to be used for different purposes.