Isabel Hilber

Quantitative determination of PAHs in biochar: a prerequisite to ensure its quality and safe application.

Biochar is increasingly promoted as a beneficial soil conditioner. However, it may contain residues of polycyclic aromatic hydrocarbons (PAHs) as a result of its production by pyrolysis. To date, analytical methods to analyze PAHs in biochar quantitatively are hardly available. This study presents an optimized and validated procedure to quantify the 16 U.S. EPA PAHs in biochar. PAHs were best extracted with Soxhlet for 36 h using 100% toluene. Average absolute recoveries of isotope labeled internal standards used for each analyte from three different biochars ranged from 42% to 72%, and relative recoveries were between 71% and 105%. The limits of detection were biochar-dependent, but on average a factor of >50 lower than quantified PAH concentrations (9-355 mg kg(dry weight)(-1)). The established method prepares the ground for a harmonized protocol for PAH analysis of biochars, a necessity for biochar quality control, registration, and legislation.

Influence of activated charcoal amendment to contaminated soil on dieldrin and nutrient uptake by cucumbers.

Activated charcoal (AC) amendments have been suggested as a promising, cost-effective method to immobilize organic contaminants in soil. We performed pot experiments over two years with cucumber (Cucumis sativus L.) grown in agricultural soil with 0.07 mg kg(-1) of weathered dieldrin and 0, 200, 400, and 800 mg AC per kg soil. Dieldrin fresh weight concentrations in cucumber fruits were significantly reduced from 0.012 to an average of 0.004 mg kg(-1), and total uptake from 2 to 1 microg in the 800 mg kg(-1) AC treatment compared to the untreated soil. The treatment effects differed considerably between the two years, due to different meteorological conditions. AC soil treatments did neither affect the availability of nutrients to the cucumber plants nor their yield (total fruit wet weight per pot). Thus, some important prerequisites for the successful application of AC amendments to immobilize organic pollutants in agricultural soils can be considered fulfilled.

Toward the Standardization of Biochar Analysis: The COST Action TD1107 Interlaboratory Comparison

Biochar produced by pyrolysis of organic residues is increasingly used for soil amendment and many other applications. However, analytical methods for its physical and chemical characterization are yet far from being specifically adapted, optimized, and standardized. Therefore, COST Action TD1107 conducted an interlaboratory comparison in which 22 laboratories from 12 countries analyzed three different types of biochar for 38 physical-chemical parameters (macro- and microelements, heavy metals, polycyclic aromatic hydrocarbons, pH, electrical conductivity, and specific surface area) with their preferential methods. The data were evaluated in detail using professional interlaboratory testing software. Whereas intralaboratory repeatability was generally good or at least acceptable, interlaboratory reproducibility was mostly not (20% < mean reproducibility standard deviation < 460%). This paper contributes to better comparability of biochar data published already and provides recommendations to improve and harmonize specific methods for biochar analysis in the future.

How to Determine the Environmental Exposure of PAHs Originating from Biochar

Biochars are obtained by pyrolyzing biomass materials and are increasingly used within the agricultural sector. Owing to the production process, biochars can contain polycyclic aromatic hydrocarbons (PAHs) in the high mg/kg range, which makes the determination of the environmental exposure of PAHs originating from biochars relevant. However, PAH sorption to biochar is characterized by very high (10(4)-10(6) L/kg) or extreme distribution coefficients (KD) (>10(6) L/kg), which makes the determination of exposure scientifically and technically challenging. Cyclodextrin extractions, sorptive bioaccessibility extractions, Tenax extractions, contaminant traps, and equilibrium sampling were assessed and selected methods used for the determination of bioavailability parameters for PAHs in two model biochars. Results showed that: (1) the KD values of typically 10(6)-10(9) L/kg made the biochars often act as sinks, rather than sources, of PAHs. (2) Equilibrium sampling yielded freely dissolved concentrations (pg-ng/L range) that were below or near environmental background levels. (3) None of the methods were found to be suitable for the direct measurement of the readily desorbing fractions of PAHs (i.e., bioacessibility) in the two biochars. (4) The contaminant-trap method yielded desorption-resistant PAH fractions of typically 90-100%, implying bioaccessibility in the high μg/kg to low mg/kg range.

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.

Assessing the Phytoavailability of Dieldrin Residues in Charcoal-Amended Soil Using Tenax Extraction

Consecutive and single Tenax extractions were applied to characterize the effectiveness of activated charcoal (AC) amendments to reduce the phytoavailability of dieldrin in a natively contaminated horticultural soil. Dieldrin desorption from untreated and 800 mg(AC) kg(-1) soil was well described by a model with three dieldrin fractions of different kinetics: a rapidly (F(rap)), slowly (F(slow)), and very slowly (F(v.slow)) desorbing fraction. The AC amendment resulted in a transfer of dieldrin from the F(slow) to the F(v.slow) fraction. The F(v.slow) increased by nearly 10% compared to the control soil. Dieldrin extractability by Tenax from AC amended soils was not influenced by the cultivation of cucumber plants indicating the stability of this remediation technique. Dieldrin extractability by Tenax at the beginning of plant growth correlated only weakly with the dieldrin content of the cucumbers at harvest. Therefore, the potential of Tenax extractions to predict the uptake of dieldrin by cucumbers appears to be limited.

The different faces of biochar: contamination risk versus remediation tool

This article reviews the different aspects of biochar as source and sink of organic and inorganic contaminants. Biochar can contain organic contaminants such as polycyclic aromatic hydrocarbons or ...

Applying no-depletion equilibrium sampling and full-depletion bioaccessibility extraction to 35 historically polycyclic aromatic hydrocarbon contaminated soils

Assessing the bioaccessibility of organic pollutants in contaminated soils is considered a complement to measurements of total concentrations in risk assessment and legislation. Consequently, methods for its quantification require validation with historically contaminated soils. In this study, 35 such soils were obtained from various locations in Switzerland and Cuba. They were exposed to different pollution sources (e.g., pyrogenic and petrogenic) at various distance (i.e., urban to rural) and were subject to different land use (e.g., urban gardening and forest). Passive equilibrium sampling with polyoxymethylene was used to determine freely dissolved concentrations (Cfree) of polycyclic aromatic hydrocarbons (PAHs), while sorptive bioaccessibility extraction (SBE) with silicone rods was used to determine the bioaccessible PAH concentrations (Cbioacc) of these soils. The organic carbon partition coefficients of the soils were highest for skeet soils, followed by traffic, urban garden and rural soils. Lowest values were obtained from soil exposed to petrogenic sources. Applicability of SBE to quantify Cbioacc was restricted by silicone rod sorption capacity, as expressed quantitatively by the Sorption Capacity Ratio (SCR); particularly for soils with very high KD. The source of contamination determined bioaccessible fractions (fbioacc). The smallest fbioacc were obtained with skeet soils (15%), followed by the pyrogenically influenced soils, rural soils, and finally, the petrogenically contaminated soil (71%). In conclusion, we present the potential and limitations of the SBE method to quantify bioaccessibility in real soils. These results can be used for additional development of this and similar bioaccessibility methods to guarantee sufficient sorption capacity to obtain reliable results.

Comparison of freely dissolved concentrations of PAHs in contaminated pot soils under saturated and unsaturated water conditions

Passive sampling (PS, equally used for passive sampler) methods have successfully been applied in situ to quantify the bioavailability of hydrophobic organic compounds in air, water and sediments. However, very little is known on the applicability of PS in unsaturated soils. Here, we present the results of a greenhouse experiment in which we applied in situ PS methods in pots. Low density polyethylene (LDPE) and polydimethylsiloxane (PDMS) fibres with a newly developed PS holder were used to analyse freely dissolved polycyclic aromatic hydrocarbon (PAH) concentrations (Cfree) in a skeet shooting range soil and an uncontaminated control soil under water saturated and unsaturated conditions for up to nine months. A short exposure time of three months was not sufficient for the PDMS samplers to reach distribution equilibrium with the surrounding soil. Under saturated water conditions, the in situ results agreed well with measurements obtained from the conventional ex situ soil suspension method. They were in accordance with similar comparisons made in previous studies on sediments, as well as with model predictions. However, for unsaturated water conditions, the results differed considerably from the ex situ Cfree values, in particular for the light molecular weight (LMW) PAHs such as phenanthrene, fluoranthene, and pyrene. The results of the two in situ PS methods were in good agreement with each other under both soil water conditions, indicating that dissipation mechanisms, such as degradation or volatilization, led to a substantial decrease in Cfree under unsaturated conditions, especially for the LMW PAHs (log10KOW < 5.85) over a period of six months or more. Thus, in their current state of development, in situ PS methods can be used in soils under water-saturated conditions. However, an adequate method to correct for non-equilibrium conditions needs to be developed before they can be applied to unsaturated conditions, mainly for LMW PAHs.