Synthesis of biochar from residues after biogas production with respect to cadmium and nickel removal from wastewater.

The objective of the study was to investigate the ability of biochars prepared under different temperatures (400 °C and 600 °C) from the residue of biogas production (RBP) for the adsorption of cadmium (Cd(II)) and nickel (Ni(II)) ions from aqueous solution. Furthermore, the RBP biochars adsorption capacity was compared with adsorption capacity of biochar produced from wheat straw at 600 °C (BCS600). The kinetics of the adsorption, the sorption isotherms, the influence of solution pH and the interfering ions (chlorides and nitrates) were investigated. The desorption of Cd(II) and Ni(II) by hydrochloric and nitric acid from biochars was also investigated. The different types of feedstock used for biochar (BC) preparation (RBP and biomass) determined the physico-chemical properties of biochars and hence their adsorption abilities. Generally, biochars produced from RBPs (regardless of temperature) had the greater capacity to adsorb Cd(II) and Ni(II) than the biochar produced from wheat straw. Of the tested models (Freundlich and Langmuir), the Langmuir model was demonstrated to be the best to describe the sorption of Cd(II) and Ni(II). For the kinetic study, the adsorption process proceeded the fastest for BCU400 than BCU600. Furthermore, BCU600 was the most resistant to the influence of interfering ions on adsorption. For the desorption study, BCU400 was characterized by the highest reproducibility of the surface. The comparison of the results obtained in each adsorption step between RBP biochars and BCS600 suggested that the residue from biogas production could be successfully applied for the removal of Cd(II) and Ni(II) ions from aqueous solutions.

A field study of bioavailable polycyclic aromatic hydrocarbons (PAHs) in sewage sludge and biochar amended soils.

The bioavailable PAHs (freely dissolved concentration, Cfree) were determined in sewage sludge (SL) or sewage sludge and biochar (BC) amended soil. SL or SL with a 2.5, 5 or 10% of BC was applied to the soil. The study was conducted as a long-term field experiment. Addition of BC to SL at a dose of 2.5 and 5% did not affect the content of Cfree PAHs in soils. However a significant difference (by 13%) in Cfree PAHs content was noted in experiment with 10% addition of BC. During the experiment, the concentration of Cfree PAHs in SL- and SL/BC-amended soil decreased. In particular sampling terms the content of Cfree PAHs in SL/BC-amended soil was significantly lower comparing to the Cfree PAHs content in SL-amended soil. After 18 months, Cfree PAH content was significantly lower in SL/BC-amended soil than in the experiment with SL alone, and did not differ significantly from the Σ16 Cfree content in the control soil. The largest decrease relative to the soil with sewage sludge alone was observed for 3-, 5- and 6-ring PAHs. This is the first field-based evidence that biochar soil amendment was effective to reduce of the Cfree of PAHs in sewage sludge-amended soils.

Co-application of sewage sludge with biochar increases disappearance of polycyclic aromatic hydrocarbons from fertilized soil in long term field experiment.

The application of sewage sludge with biochar as fertilizer may be a new method improves soil properties. Biochar increases of the crops productivity and reduction of bioavailability of contaminants. In the present study the persistence of sum of 16 (Σ16) PAHs (US EPA 16 PAHs) in a sewage sludge-amended soil (11t/h) and in a sewage sludge-amended soil with the addition of biochar (at a rate of 2.5, 5 or 10% of sewage sludge (dry weight basis)) was determined. This study was carried out as a plot experiment over a period of 18months. Samples for analysis were taken at the beginning of the study and after 6, 12 and 18months from the beginning of the experiment. Application of sewage sludge as a soil amendment did not cause a significant change (P≥0.05) in the soil content of Σ16 PAHs. In turn, the addition of biochar with sewage sludge to the soil, regardless of the contribution of biochar in the sewage sludge, resulted in a significant decrease in PAH content already at the beginning of the experiment. Throughout the experiment, in all treatments the PAH content varied, predominantly showing a decreasing trend. Ultimately, after 18months the content of Σ16 PAHs decreased by 19% in the experiment with sewage sludge alone and by 45, 35 and 28% in the experiment with sewage sludge and the 2.5%, 5.0% and 10% biochar rates, respectively. After 18months of the study, the largest losses in the sewage sludge-amended soil were observed for 2- and 3-ring PAHs. In the sewage sludge- and biochar-amended soil, compared to the beginning of the study and the sewage sludge-amended soil, the highest losses were found for 5- and 6-ring PAHs (2.5 and 5.0% rates) as well as for 5- and 2-ring PAHs (10% rate).

The total and freely dissolved polycyclic aromatic hydrocarbons content in residues from biogas production.

In the situation of increasing agricultural utilization of residues from biogas production (RBP) it is important to determine the concentration of contaminants, which could occur in these materials. The group of contaminants that requires special attention are polycyclic aromatic hydrocarbons (PAH). The objective of the study was to determine the total and freely dissolved (Cfree) of PAHs in RBP from 6 different biogas plants operating under various temperature conditions and without or with the separation into the solid and liquid fractions. The freely dissolved PAHs were determined using polyoxymethylene (POM method). The total content of the Σ16 PAHs in RBP varied from 449 to 6147 µg/kgdw, while that of Cfree PAHs was at the level from 57 to 653 ng/L. No significant differences were noted in the content of the Σ16 PAHs (total) between the solid and the liquid fractions. This indicates that in the course of the separation, the PAHs are distributed proportionally between the fractions. However in the case of Cfree, PAHs content in the solid fraction was over twice as high as in the liquid fraction. This was probably due to the greater affinity of the particles present in the liquid fraction to the analysed PAHs than to the particles of the solid fraction. Higher affinity to liquid fraction was also confirmed by the distribution coefficients KTOC determined on the basis of Cfree.

Addition of biochar to sewage sludge decreases freely dissolved PAHs content and toxicity of sewage sludge-amended soil.

Due to an increased content of polycyclic aromatic hydrocarbons (PAHs) frequently found in sewage sludges, it is necessary to find solutions that will reduce the environmental hazard associated with their presence. The aim of this study was to determine changes of total and freely dissolved concentration of PAHs in sewage sludge-biochar-amended soil. Two different sewage sludges and biochars with varying properties were tested. Biochars (BC) were produced from biogas residues at 400 °C or 600 °C and from willow at 600 °C. The freely dissolved PAH concentration was determined by means of passive sampling using polyoxymethylene (POM). Total and freely dissolved PAH concentration was monitored at the beginning of the experiment and after 90 days of aging of the sewage sludge with the biochar and soil. Apart from chemical evaluation, the effect of biochar addition on the toxicity of the tested materials on bacteria - Vibrio fischeri (Microtox®), plants - Lepidium sativum (Phytotestkit F, Phytotoxkit F), and Collembola - Folsomia candida (Collembolan test) was evaluated. The addition of biochar to the sewage sludges decreased the content of Cfree PAHs. A reduction from 11 to 43% of sewage sludge toxicity or positive effects on plants expressed by root growth stimulation from 6 to 25% to the control was also found. The range of reduction of Cfree PAHs and toxicity was dependent on the type of biochar. After 90 days of incubation of the biochars with the sewage sludge in the soil, Cfree PAHs and toxicity were found to further decrease compared to the soil with sewage sludge alone. The obtained results show that the addition of biochar to sewage sludges may significantly reduce the risk associated with their environmental use both in terms of PAH content and toxicity of the materials tested.

Chemical and ecotoxicological evaluation of biochar produced from residues of biogas production.

Analyses were carried out for biochars produced at three temperatures of pyrolysis (400, 600 and 800°C) from solid residue from biogas production (RBP). Separated and non-separated RBP from biogas plants employing different biogas production conditions were pyrolyzed. The contents of heavy metals and polycyclic aromatic hydrocarbons (PAHs) (16 PAH US EPA) were analyzed in biochars. The analyses showed that with an increased pyrolysis temperature, there was an increase in the contents of PAHs and of certain heavy metals (Cr, Cu, Cd, Pb and Mn). In the ecotoxicological tests, it was noted that the effect depended on the temperature of pyrolysis and on the feedstock from which the biochar was produced. The least harmful effect on the test organisms was from biochar produced by separated RBP in a biogas plant operating in mesophilic conditions. The most negative effect on the test organisms was characteristic of biochar produced from non-separated mesophilic RBP. This study shows that the main factors determining the level of toxicity of biochars produced from RBP towards various living organisms are both the method of feedstock production and the temperature at which the process of pyrolysis is conducted.

Ecotoxicological assessment of residues from different biogas production plants used as fertilizer for soil.

Residues from biogas production (RBP) are a relatively new materials, which may be an interesting resource for the improvement of soil fertility. Nevertheless, in spite of the potential benefits from the agricultural utilization of RBP, there is a need of comprehensive estimation of their toxicity. This information is needed to exclude potential negative environmental impacts arising from the use of RBP. Samples of RBP obtained from six biogas production plants with varied biogas production methods were analysed. The samples with and without separation on solid and liquid phases were investigated. The physicochemical properties of the RBP, heavy metals content (Cr, Cu, Ni, Cd, Pb i Zn) and toxicity on bacteria (Vibrio fischeri, MARA test - 11 different strains), collembolans (Folsomia candida) and two plant species (Lepidium sativum and Sinapis alba) was investigated. Toxicity of RBP was examined using Phytotoxkit F (root growth inhibition), collembolan test (mortality, inhibition of reproduction), Microtox® (inhibition of the luminescence of V. fischeri) and MARA test (growth of microorganisms). An especially negative effect on the tested organisms whereas was noted for the liquid phase after separation. In many cases, RBP without separation also showed unfavourable effects on the tested organisms. Liquid phase after separation and non-separated materials caused inhibition of root growth of L. sativum and S. alba at the level of 17.42-100% and 30.5-100%, respectively, as well as the inhibition of reproduction of F. candida with the range from 68.89 to 100%. In most cases, no ecotoxicological effect was observed for solid phase after separation for tested organisms. The solid phase after separation presented the most favorable properties between all investigated RBP. Therefore, it can be a potential material for the improvement of soil properties and for later use in agriculture.