Changes of total and freely dissolved polycyclic aromatic hydrocarbons and toxicity of biochars treated with various aging processes.

The aim of this study was to determine the effect of biochar aging on the content of polycyclic aromatic hydrocarbons (PAHs) (the total content - Ctot, and the freely dissolved - Cfree) in biochar and its ecotoxicity. Two biochars (BCS and BCM) with varying properties were aged for 420 days at different temperatures (-20 °C, 4 °C, 20 °C, 70 °C), at a variable temperature (-20/20 °C), in the presence of nutrients, and in the presence of inoculum and nutrients. After the aging process, Ctot and Cfree PAHs were determined in samples obtained and an ecotoxicological analysis was performed, which involved tests with bacteria (Vibrio fischeri), invertebrates (Folsomia candida) and plants (Lepidium sativum). Aging significantly affected all the parameters tested. The range of changes in the studied parameters depended on the type of biochar and ageing conditions. In the case of most of the aging methods, PAH content (Ctot, Cfree) and toxicity were found to decrease. Aging in the presence of microorganisms and nutrients and in the presence of nutrients alone caused the greatest reduction in Ctot PAH content (a reduction from 30 to 100% relative to non-aged biochar), Cfree PAH content (a reduction from 12 to 100%), root growth inhibition (a reduction from 73 to 90%), and luminescence inhibition (a reduction from 24 to 100%). In the case of Cfree PAHs and toxicity to F. candida, some aging methods caused their increase. The study also found a significant relationship between the changes in Ctot PAH content during aging and inhibition of root growth (BCS, BCM) and inhibition of V. fischerii luminescence (BCM). In no case was a significant correlation (P ≥ 0.05) between Cfree PAHs and the investigated toxicity parameters found.

Effect of co-application of nano-zero valent iron and biochar on the total and freely dissolved polycyclic aromatic hydrocarbons removal and toxicity of contaminated soils.

The aim of this study was to investigate co-application of biochar and nano zero-valent iron (nZVI) in order to increase the degradation of PAHs and reduce the toxicity of soils historically contaminated with these compounds. To performed the experiment biochar, biochar with nZVI (2 g kg-1 or 10 g kg-1 soil), or nZVI alone (2 g kg-1 or 10 g kg-1 soil) were added to the PAHs contaminated soils. The soils alone and soils with amendments were aged by mixing for 7 and 30 days. After that the chemical analysis were carried out and total (Ctot) and Cfree PAH content in the samples were determined. Moreover, the toxicity of aqueous extracts were investigated using the Microtox® (Vibrio fischeri) method. Results showed that any of used nZVI dose did not reduce the content of Ctot or Cfree PAHs in contaminated soils, but biochar applied both alone and together with the nZVI significantly reduced Ctot and Cfree PAHs. However, no significant differences in PAH reduction were found between biochar alone and biochar with nZVI addition. This indicates that the observed reduction was mostly associated with the sorption properties of biochar. Moreover, only in the case of co-application of biochar and nZVI reduction of the toxicity of nZVI to V. fischeri was observed. The toxic effect was different and depend on the type of soil and their properties including total organic carbon and black carbon content, which may affect the PAHs reduction efficiency.

Effect of biochar activation by different methods on toxicity of soil contaminated by industrial activity.

The objective of the study was to determine the effect of various methods of biochar activation on the ecotoxicity of soils with various properties and with various content and origin of contaminants. The biochar produced from willow (at 700°C) was activated by 1) microwaves (in a microwave reactor under an atmosphere of water vapour), 2) carbon dioxide (in the quartz fluidized bed reactor) and 3) superheated steam (in the quartz fluidized bed reactor). Three different soils were collected from industrial areas. The soils were mixed with biochar and activated biochars at the dose of 5% and ecotoxicological parameters of mixture was evaluated using two solid phase test - Phytotoxkit F (Lepidium sativum) and Collembolan test (Folsomia candida) and one liquid phase test - Microtox® (Vibrio fischeri). Biochar activation had both positive and negative impacts, depending on the activation method, kind of bioassay and kind of soil. Generally, biochar activated by microwaves increased the effectiveness of ecotoxicity reduction relative to non-activated biochars. Whereas, biochar activated with CO2 most often cause a negative effect manifested by deterioration or as a lack of improvement in relation to non-activated biochar or to non-amended soil. It was also demonstrated that the increase of biochar specific surface area caused a significant reduction of toxicity of water leachates from the studied soils. Effectiveness of the reduction of leachate toxicity was weakened in the presence of dissolved organic carbon in the soil.

Effect of steam activated biochar application to industrially contaminated soils on bioavailability of polycyclic aromatic hydrocarbons and ecotoxicity of soils.

The aim of this study was to determine the effect of steam activation of biochars on the immobilization of freely dissolved (Cfree) and bioaccessible fraction (Cbioacc) of PAHs in soils. Additionally, the toxicity to various organisms like Vibrio fischeri, Lepidium sativum and Folsomia candida was measured before and after the amendment of biochars to soils. Three biochars produced from willow, coconut and wheat straw were steam activated and added to three different soils with varying content and origin of PAHs (coke vs. bitumen). The soils with the addition of the biochars (activated and non-activated) were incubated for a period of 60days. Steam activation of the biochars resulted in more pronounced reduction of both Cfree and Cbioacc. The range of the increase in effectiveness was from 10 to 84% for Cfree and from 50 to 99% for Cbioacc. In contrast, the effect of activation on the toxicity of the soils studied varied greatly and was specific to a particular test and soil type. Essentially, biochar activation did not result in a change of phytotoxicity, but it increased or decreased (depending on the parameter, type of biochar, contaminant source, and soil and soil type) the toxic effect to F. candida, and decreased the toxicity of leachates to V. fischeri.

Effect of activated carbon and biochars on the bioavailability of polycyclic aromatic hydrocarbons in different industrially contaminated soils.

Coal production negatively affects the environment by the emission of polycyclic aromatic hydrocarbons (PAHs). Two soils (KOK and KB) from a coking plant area was investigated and their total PAH concentration was 40 and 17 mg/kg for the sum (∑) 16 US EPA PAHs, respectively. A third soil was sampled from a bitumen plant area and was characterized by 9 mg/kg ∑16 US EPA PAHs. To reduce the freely dissolved concentration (Cfree) of the PAHs in the soil pore water, active carbon (AC) and two biochars pyrolysed from wheat straw (biochar-S) and willow (biochar-W) were added to the soils at 0.5-5 % (w/w), each. The AC performed best and reduced the Cfree by 51-98 % already at the lowest dose. The biochars needed doses up to 2.5 % to significantly reduce the Cfree by 44-86 % in the biochar-S and by 37-68 % in the biochar-W amended soils. The high black carbon (BC) content of up to 2.3 % in the Silesian soils competed with the sorption sites of the carbon amendments and the performance of the remediation was a consequence of the contaminant's source and the distribution between the BC and the AC/biochars. In contrast, the carbon amendment could best reduce the Cfree in the Lublin soil where the BC content was normal (0.05 %). It is therefore crucial to know the contaminant's source and history of a sample/site to choose the appropriate carbon amendment not only for remediation success but also for economic reasons.

Effect of activated carbon or biochars on toxicity of different soils contaminated by mixture of native polycyclic aromatic hydrocarbons and heavy metals.

Activated carbon (AC), biochar from wheat straw (BCS), and biochar from willow (BCW) were added to the soils sampled from areas of strong anthropogenic influence at doses of 0.5%, 1%, 2.5%, or 5% (w/w) and incubated for 2 mo. At the end of this period, the toxicity of the soils was measured. The effect of AC and biochars on the toxicity of the soils varied based on soil, type of amendment, dose, and test organism. For most of the parameters tested, the highest effectiveness of AC in terms of reduction of toxicity was observed in soil POPI (from bitumen processing plant area). In the case of the remaining soils, after the addition of AC varied results were observed, in which a reduction or an increase of toxicity, relative to the control soil, occurred. As in the case of AC, biochars also caused a significant reduction of phytotoxicity of soil POPI. In soils KB (from coking plant area, industrial waste deposit) and KOK (from coking plant area, coking battery), the reduction or increase of toxicity depended on biochar dose. Compared with the biochars, the effectiveness of AC in the reduction of toxicity depended also on soil, type of amendment, dose, and test organism. Generally, the AC was more effective than biochars in relation to mortality and reproduction of Folsomia candida (in all soils) and for reduction of luminescence inhibition of Vibrio fischeri (in POPI soil).