Leaching and Geochemical Modelling of an Electric Arc Furnace (EAF) and Ladle Slag Heap.

Old metallurgical dumps across Europe represent a loss of valuable land and a potential threat to the environment, especially to groundwater (GW). The Javornik electric arc furnace (EAF) and ladle slag heap, situated in Slovenia, was investigated in this study. The environmental impact of the slag heap was evaluated by combining leaching characterization tests of landfill samples and geochemical modelling. It was shown that throughout the landfill the same minerals and sorptive phases control the leaching of elements of potential concern, despite variations in chemical composition. Although carbonation of the disposed steel slags occurred (molar ratio CO3/(Ca+Mg) = 0.53) relative to fresh slag, it had a limited effect on the leaching behaviour of elements of potential concern. The leaching from the slag heaps had also a limited effect on the quality of the GW. A site-specific case, however, was that leachates from the slag heap were strongly diluted, since a rapid flow of GW fed from the nearby Sava River was observed in the landfill area. The sampling and testing approach applied provides a basis for assessing the long-term impact of release and is a good starting point for evaluating future management options, including beneficial uses for this type of slag.

Physico-Chemical Properties of the Pyrolytic Residue Obtained by Different Treatment Conditions of Meat and Bone Meal.

The depletion of phosphate rock reserves has led to the search for new, alternative and environmentally friendly products and processes. One of the safe and environmentally friendly sources of phosphate is animal bone char (ABC), the residue from the pyrolysis of meat and bone meal (MBM), a slaughterhouse waste material. The presented study investigated the physico-chemical properties of the residues (ABC) obtained from the pyrolysis of MBM under different treatment conditions. Two different end temperatures (600 °C and 1000 °C) and five different heating rates (5 °C min-1, 10 °C min-1, 20 °C min-1, 50 °C min-1 and 100 °C min-1) were used. The ABC samples obtained were characterised by X-ray powder diffraction, IR spectroscopy, elemental CHNS analysis and SEM/EDS analysis. The results showed the strong influence of both the pyrolysis end temperature and the heating rate on the morphology and chemical composition of the final products.

An extensive characterization of various environmentally relevant microplastics - Material properties, leaching and ecotoxicity testing.

Microplastics in the environment occur in different sizes and shapes and are made of various polymers. Therefore, they also considerably differ in their properties and ecotoxicity. However, the majority of microplastics research uses pre-made spherical microplastics, which practically do not exist in the environment. Our work focused on a comprehensive study of six different types of microplastic that were prepared to simulate common microplastics found in the environment. All types of microplastics where chemically and physically characterized using Fourier-transform infrared spectroscopy, thermal analysis, field-emission scanning electron microscopy, optical microscopy and laser diffraction analysis. The specific surface area was determined using the BET method. Furthermore, effects of microplastics and microplastic leachates on a common duckweed (Lemna minor) were evaluated. All tested microplastics did not affect specific growth rate and chlorophyll a content in duckweed, while microplastics with a rough surface and sharp edges caused a significant reduction of duckweed root length. Microplastics made of Bakelite also showed an intensive leaching, which increased their ecotoxicity potential. Natural particles used as a control did not have any negative effect on duckweed. Overall, microplastic particles have significantly different ecotoxicity profiles depending on their physico-chemical properties. Therefore, the testing of environmentally relevant particles and their proper characterization, as well as the testing of microplastic leaching properties, is crucial for understanding of microplastics ecotoxicological potential.

Oral and inhalation bioaccessibility of potentially toxic elements in household dust from former Hg mining district, Idrija, Slovenia.

One of the main sources of potential chronic exposure to potentially toxic elements is household dust, especially in an environment with known point sources of PTE pollution. The literature review clearly shows that the total concentrations of an element in the environment do not provide information to predict its bioavailability. The aim of the present study was to evaluate the oral and inhalation bioaccessibility of PTE present in household dust in the small town of Idrija, the site of the former mercury mine. Unified bioaccessibility method was used to assess oral bioaccessibility of PTE in the stomach and intestine, while inhalation bioaccessibility was assessed by extraction of household dust samples with two synthetic extraction solutions-Gamble's solution (GS) and artificial lysosomal fluid (ALF). A low bioaccessibility of mercury was observed in all synthetic solutions (less than 3%). The highest bioaccessibility of PTE was observed in ALF solution, especially for Zn, Pb and Cd. Only a slightly lower bioaccessibility of these three elements was also observed in the stomach, while the bioaccessibility of other elements in the gastric phase was less than 40%. In general, the bioaccessibility of all elements decreased in the intestine. With the exception of Cr, the lowest bioaccessibility of the elements was observed in GS. Daily ingestion and inhalation doses of PTE from household dust were calculated and their values were below the available recommended or tolerable daily intakes of PTE from food according to the European Food Safety Authority.

Preliminary Evaluation of Animal Bone Char as Potential Metal Stabilization Agent in Metal Contaminated Soil.

The aim of this study was to evaluate the potential effect of animal bone char (ABC) addition on metal mobility in mine tailings. The mobility of metals after addition of ABC to tailings at four different application rates (0.6 g, 1.2 g, 1.8 g and 3.6 g ABC per 100 g of tailings) was evaluated by Toxicity Characteristic Leaching Procedure (TCLP) one step extraction. The obtained results indicated that the mobility of Pb, Cr and Cd gradually decreased with increasing quantity of added ABC. According to the TCLP, mobile concentrations of Pb in tailings exceeded threshold values for almost eight times. After ABC addition, Pb TCLP-extractable concentrations decreased from 39 mg L-1 in tailings to lower than the TCLP limit values of 5 mg L-1 at all ABC application rates, except in mixtures with the lowest addition of ABC. We concluded that ABC could be a successful metal stabilization agent for multi-metal contaminated soil, although attention should be paid at highly As contaminated soil.

Study of the leaching behaviour of ladle slags by means of leaching tests combined with geochemical modelling and mineralogical investigations.

In this study, the leachability of freshly produced ladle slag derived from both austenitic and ferritic stainless steel production, and from electrical and structural steel production, was investigated, in order to determine whether variations in the chemical and mineralogical composition of these slags affect their leaching behaviour. The effect of the method used for slag cooling was also studied. The results obtained by using the single batch test were combined with those obtained by means of more sophisticated characterisation leaching tests, which, in combination with geochemical speciation modelling, helped to better identify the release mechanisms and phases that control the release of individual elements. It was found that, although variations in the chemical composition of the slag can affect the slag's minerology, neither such variations, nor the choice of the slag cooling treatment, have a significant effect on the leachability of individual elements, since the leaching is governed by surface phenomena. In fact, the mineral transformations on the slag surface, rather than the bulk mineral composition, dictate the release of these elements from the ladle slag. The solubility-controlling phases were predicted by multi-element modelling, and verified to the extent made possible by the performed mineralogical investigations.

The impact of humic acid on chromium phytoextraction by aquatic macrophyte Lemna minor.

Studies assessing chromium phytoextration from natural waters rarely consider potential implications of chromium speciation in the presence of ubiquitous humic substances. Therefore, the present study investigated the influence of environmentally relevant concentration of humic acid (TOC = 10 mg L(-1)) on chromium speciation (Cr = 0.15 mg L(-1)) and consequently on phytoextraction by aquatic macrophyte duckweed Lemna minor. In absence of humic acid, only hexavalent chromium was present in water samples and easily taken up by L. minor. Chromium uptake resulted in a significant reduction of growth rate by 22% and decrease of chlorophyll a and chlorophyll b contents by 48% and 43%, respectively. On the other hand, presence of humic acid significantly reduced chromium bioavailability (57% Cr uptake decrease) and consequently it did not cause any measurable effect to duckweed. Such effect was related to abiotic reduction of hexavalent chromium species to trivalent. Hence, findings of our study suggest that presence of humic acid and chromium speciation cannot be neglected during phytoextraction studies.

Application of multiple toxicity tests in monitoring of landfill leachate treatment efficiency.

Leachate from a closed landfill used for co-disposal of municipal and tannery waste was submitted to coagulation treatment, air stripping, adsorption on granular activated carbon, and Fenton oxidation with the aim to reduce toxicity of the leachate. Optimal operational conditions for each process were identified. The performance of the treatment was monitored by determination of organic matter (COD, DOC, BOD5), inorganic components (N-NH4(+), Cl(-), alkalinity, metals), organic compounds (BTEX, PAHs, PCBs, OCPs) while changes in toxicity were followed by multiple toxicity tests. Among the applied treatment techniques, adsorption on granular activated carbon was the most efficient method for removal of organic matter and metals while air stripping was the most efficient for removal of N-NH4(+) and reduction of toxicity. Lower reduction of organic matter content and toxicity was obtained during coagulation treatment. Fenton oxidation was effective for removal of COD; however, it negatively affected toxicity reduction. The combination of adsorption on granular activated carbon and air stripping led to an appreciable reduction of organic and inorganic pollutants and to leachate detoxification. Application of bioassays was helpful for assessing suitability of treatment methods and demonstrated that they are, together with physicochemical parameters, an indispensable part for monitoring of treatment efficiency.

Possible time-dependent effect of ions and hydrophilic surfaces on the electrical conductivity of aqueous solutions.

The purpose of this work was to determine the influence of mechanical and electrical treatment on the electrical conductivity of aqueous solutions. Solutions were treated mechanically by iteration of two steps: 1:100 dilution and vigorous shaking. These two processes were repeated until extremely dilute solutions were obtained. For electrical treatment the solutions were exposed to strong electrical impulses. Effects of mechanical (as well as electrical) treatment could not be demonstrated using electrical conductivity measurements. However, significantly higher conductivity than those of the freshly prepared chemically analogous solutions was found in all aged solutions except for those samples stored frozen. The results surprisingly resemble a previously observed weak gel-like behavior in water stored in closed flasks. We suggest that ions and contact with hydrophilic glass surfaces could be the determinative conditions for the occurrence of this phenomenon.

Metal immobilization and phosphorus leaching after stabilization of pyrite ash contaminated soil by phosphate amendments.

In this study we would like to show the importance of a holistic approach to evaluation of chemical stabilization using phosphate amendments. An extensive evaluation of metal stabilization in contaminated soil and an evaluation of the leaching of phosphorus induced after treatment were performed. The soil was highly contaminated with Cu (2894 mg kg(-1)), Zn (3884 mg kg(-1)), As (247 mg kg(-1)), Cd (12.6 mg kg(-1)) and Pb (3154 mg kg(-1)). To immobilize the metals, mixtures of soil with phosphate (from H(3)PO(4) and hydroxyapatite (HA) with varying ratios) were prepared with a constant Pb : P molar ratio of 1: 10. The acetic acid extractable concentration of Pb in the mixture with the highest amount of added phosphoric acid (n(H(3)PO(4)) : n(HA) = 3 : 1) was reduced to 1.9% (0.62 mg L(-1)) of the extractable Pb concentration in the untreated soil, but the content of water extractable phosphorus in the samples increased from 0.04 mg L(-1) in the untreated soil sample up to 14.3 mg L(-1) in the same n(H(3)PO(4)) : n(HA) = 3 : 1 mixture. The high increase in arsenic mobility was also observed after phosphate addition. The PBET test showed phosphate induced reduction in Pb bioavailability. In attempting to stabilize Pb in the soil with the minimum treatment-induced leaching of phosphorus, it was found that a mixture of soil with phosphate addition in the molar ratio of H(3)PO(4) : HA of 0.75 : 1 showed the most promising results, with an acetic acid extractable Pb concentration of 1.35 mg L(-1) and a water extractable phosphorus concentration of 1.76 mg L(-1). The time-dependent leaching characteristics of metals and phosphorus for this mixture were evaluated by a column experiment, where irrigation of the soil mixture with the average annual amount of precipitation in Slovenia (1000 mm) was simulated. The phosphorus concentration in the leachates decreased from 2.60 mg L(-1) at the beginning of irrigation to 1.00 mg L(-1) at the end.

Phytoremediation of landfill leachate and compost wastewater by irrigation of Populus and Salix: Biomass and growth response.

A pot experiment is described with a fast-growing poplar clone and two native willows (Populus deltoides Bartr. cl. I-69/55 (Lux)), Salix viminalis L. and Salix purpurea L.), irrigated with landfill leachate and compost wastewater over a 1-year growing period. The use of leachate resulted in up to 155% increased aboveground biomass compared to control water treatments and in up to 28% reduced aboveground biomass compared to a complete nutrient solution. The use of compost wastewater resulted in up to 62% reduced aboveground biomass compared to the control treatments and in up to 86% reduced aboveground biomass compared to the complete nutrient solution. Populus was the most effective in biomass production due to the highest leaf production, whereas S. purpurea was the least effective in biomass accumulation, but less sensitive to high ionic strength of the irrigation water compared to S. viminalis. The results showed a high potential for landfill leachate application (with up to 2144 kg N ha(-1), 144 kg P ha(-1), 709 kg K ha(-1), 1010 kg Cl ha(-1), and 1678 kg Na ha(-1) average mass load in the experiment). High-strength compost wastewater demonstrated less potential for application as irrigation and fertilization source even in high water-diluted treatments (1:8 by volume).

Fate of saline ions in a planted landfill site with leachate recirculation.

Recirculation of leachate on a covered landfill site planted with willows or other highly evapotranspirative woody plants is an inexpensive option for leachate management. In our study, a closed landfill leachate recirculation system was established on a rehabilitated municipal solid waste landfill site with planted landfill cover. The main objective of the study was to evaluate the sustainability of the system with regard to high hydraulic loads of the landfill leachate on the landfill cover and high concentrations of saline ions, especially potassium (K(+)), sodium (Na(+)) and chloride (Cl(-)), in leachate. The results of intensive monitoring, implemented during May 2004 and September 2007, including leachate, soil and plant samples, showed a high sustainability of the system regarding saline ions with the precipitation regime of the studied region. Saline ion concentrations in leachates varied between 132 and 2592mg Cl(-) L(-1), 69 and 1310mg Na(+) L(-1) and between 66 and 2156mg K(+) L(-1), with mean values of 1010, 632 and 686mg L(-1), respectively. Soil salinity, measured as soil electrical conductivity (EC), remained between 0.17 and 0.38mS cm(-1) at a depth between 0 and 90cm. An average annual precipitation of 1000mm provided sufficient leaching of saline ions, loaded by irrigation with landfill leachate, from the soil of the landfill cover and thus prevented possible salinity shocks to the planted willows.

Chromium in soil layers and plants on closed landfill site after landfill leachate application.

Landfill leachate (LL) usually contains low concentrations of heavy metals due to the anaerobic conditions in the methanogenic landfill body after degradation of easily degradable organic matter and the neutral pH of LL, which prevents mobilization and leaching of metals. Low average concentrations of metals were also confirmed in our extensive study on the rehabilitation of an old landfill site with vegetative landfill cover and LL recirculation after its treatment in constructed wetland. The only exception was chromium (Cr). Its concentrations in LL ranged between 0.10 and 2.75 mg/L, and were higher than the concentrations usually found in the literature. The objectives of the study were: (1) to understand why Cr is high in LL and (2) to understand the fate and transport of Cr in soil and vegetation of landfill cover due to known Cr toxicity to plants. The total concentration of Cr in LL, total and exchangeable concentrations of Cr in landfill soil cover and Cr content in the plant material were extensively monitored from May 2004 to September 2006. By obtained data on Cr concentration in different landfill constituents, supported with the data on the amount of loaded leachate, amount of precipitation and potential evapotranspiration (ETP) during the performance of the research, a detailed picture of time distribution and co-dependency of Cr is provided in this research. A highly positive correlation was found between concentrations of Cr and dissolved organic carbon (r=0.875) in LL, which indicates the co-transport of Cr and dissolved organic carbon through the system. Monitoring results showed that the substrate used in the experiment did not contribute to Cr accumulation in the landfill soil cover, resulting in percolation of a high proportion of Cr back into the waste layers and its circulation in the system. No negative effects on plant growth appeared during the monitoring period. Due to low uptake of Cr by plants (0.10-0.15 mg/kg in leaves and 0.05-0.07 mg/kg in stems of Salix purpurea), the estimated Cr offtake from LL by plants represented only a small proportion of the LL Cr mass load during the observation period, resulting in no dispersion of Cr into the environment through leaf drop.

Leachability of Cr(VI) and other metals from asphalt composites with addition of filter dust.

The potential use of filter dust in asphalt composites for road construction was investigated. Filter dust contains high concentrations of metals, of which Cr(VI) and Pb are leached with water. Compact and ground asphalt composites with addition of 2% of filter dust by mass were studied. In order to evaluate their environmental impact, leachability tests were performed using water and salt water as leaching agents. The concentrations of Cr(VI) and Pb were determined in leachates over a time period of 182 days. The results indicated that Pb was not leached with leaching agents from asphalt composites. Cr(VI) was also not leached with leaching agents from compact asphalt composites. However, in ground asphalt composites, Cr(VI) was leached with water in concentrations up to 220 microg L(-1) and in salt water up to 150 microg L(-1). From the physico-mechanical and environmental aspects, filter dust can be used as a component in asphalt mixtures.

Critical evaluation of the use of the hydroxyapatite as a stabilizing agent to reduce the mobility of Zn and Ni in sewage sludge amended soils.

The leachability of zinc (Zn) and nickel (Ni) was investigated in various soil types amended with sewage sludge and sewage sludge treated with hydroxyapatite. Sandy, clay and peat soils were investigated. For leachability tests, plastic columns (diameter 9 cm, height 50 cm) were filled with moist samples up to a height of 25 cm. Sewage sludge (1 kg) was mixed with 4.6 kg of clay and sandy soils and with 6.7 kg of peat soil. For sewage sludge mixtures treated with hydroxyapatite, 0.5 kg of the hydroxyapatite was added to 1 kg of the sewage sludge. Neutral (pH 7) and acid precipitation (pH 3.5) were applied. Acid precipitation was prepared from concentrated HNO(3), H(2)SO(4) and fresh doubly distilled water. The amount of precipitation corresponded to the average annual precipitation for the city of Ljubljana, Slovenia. It was divided into eight equal portions and applied sequentially on the top of the columns. The results indicated that the leachabilities of Zn in sewage sludge amended peat and clay soils were low (below 0.3% of total Zn content) and of Ni in sewage sludge amended sandy, clay and peat soil below 1.9% of total Ni content. In sewage sludge amended sandy soil, the leachability of Zn was higher (11% of Zn content). The pH of precipitation had no influence on the leachability of either metal. Treatment of sewage sludge with hydroxyapatite efficiently reduced the leachability of Zn in sewage sludge amended sandy soil (from 11% to 0.2% of total Zn content). In clay and peat sewage sludge amended soils, soil characteristics rather than hydroxyapatite treatment dominate Zn mobility.