Concomitant determination of pesticides in soil and drainage water over a potato cropping season reveal dissipations largely in accordance with respective models.

Pesticides are widely used in agriculture where they do not only reach their targets but also distribute to other environmental compartments and negatively affect non-target organisms. To prospectively assess their environmental risk, several tools and models using pesticide persistence (DT50) and leaching potential (groundwater ubiquity score (GUS), EXPOSIT) have been developed. Here, we simultaneously quantified 18 pesticides in soil and drainage water during a conventionally grown potato culture at field scale with high temporal resolution and compared our findings with predictions of the above models. Overall dissipations of all freshly applied compounds in soil were in line with published DT50 field values and their occurrences in drainage water were generally consistent with GUS and EXPOSIT models, respectively. In contrast, soil concentrations of the legacy pesticide atrazine and one of its transformation products (atrazine-2-hydroxy) were constant during the entire sampling campaign. Moreover, during peak discharge atrazine concentrations in drainage water were diluted whereas those of freshly applied pesticides were maximal. This difference demonstrates that the applied risk assessment tools were capable of predicting environmental concentrations and dissipation of pesticides at the short and medium time scale of a few half-lives after application, but fell short of capturing long-term trace residues.

Validation of a modified QuEChERS method for the quantification of residues of currently used pesticides in Cuban agricultural soils, using gas chromatography tandem mass spectrometry.

We present an analytical method to detect and quantify residues of currently used pesticides (CUPs), which include 31 active ingredients (ai) and seven transformation products (TPs) in tropical and agricultural soils of Cuba. Ten isotopically labeled analogous compounds served as internal standards (IL-IS). The novelty of this research is the inclusion of different tropical soils type scarcely studied for CUPs and TPs, based on the QuEChERS (quick, easy, cheap, effective, rugged and safe) method, followed by chromatography tandem mass spectrometry. All figures of merit proved to be satisfactory according to SANTE guidelines 2020 and 2021. Matrix effects (ME) calculated by the external standard method were significant (|ME| > 20% for almost all compounds; grand mean ± standard deviation (STD) 104 ± 108%) in all soils. The internal standard method compensated ME to non-significant levels (8 ± 50%), even for analytes with a non-structure identical IL-IS (STD, 13 ± 57%). Repeatability (relative standard deviation, RSDr) and reproducibility (RSDR) for skeletic regosol (SR) were 7.5 ± 2.8% and 11.7 ± 4.7%, respectively. Absolute (quantified for 11 analytes with structure identical IL-IS) and relative recovery from SR was 92 ± 13% (mean ± STD) and 90 ± 12%, respectively. Limits of quantification for SR ranged from 0.1 to 10 ng/g, except metalaxyl and oxyfluorfen (25 ng/g each). Linearity of matrix-matched (MM) calibration curves (5 to 100 ng/g) had an R2 of ≥ 0.99 for all soils and almost all analytes. The method was successfully applied to 30 real soil samples.

Pesticides in soil, groundwater and food in Latin America as part of one health.

We here report of a conference about "Pesticides in Soil, Groundwater and Food in Latin America as part of One Health" that took place at the "IV Seminario Internacional de Sanidad Agropecuaria (SISA)" in Varadero, Cuba, 8-12 May 2023. Researchers of Latin America (Argentina, Brazil, Chile, Costa Rica, Colombia, Cuba, Mexico) and Switzerland (workshop initiator) held presentations about occurrence and effects of pesticides on the environment, human health, the replacement of highly hazardous pesticides (HHP) by agroecological alternatives and the agri-food value chain. In a subsequent round table discussion, the presenters identified deficits, needs, interests and opportunities. According to them, the lack of awareness of pesticide use affects the health and safety of workers applying the chemicals. Despite Latin America representing the main agricultural area in the world with a very intense pesticide use, monitoring data of pesticides in soil, surface and groundwaters, food, as well as in humans are missing. Risks of pesticides to humans should be assessed so that authorities can withdraw or limit within "short time" the access to corresponding formulations on the market. Also, communication is not state of the art and should be improved as, e.g. the teaching of workers and farmers, how to correctly use and apply pesticides or the briefing of decision makers. Pollinators suffer from multiple stressors not the least due to pesticides, and alternatives are badly needed. On the technical side, the different analytical methods to determine residues of active ingredients and transformation products in matrices of concern should be harmonized among laboratories.Seven future actions and goals were identified to overcome the above deficits. Next steps after the publishing of this conference report are to harmonize and complete the information status of the presenters by exchanging the results/data already present. Therefore, a platform of interaction to address issues described above and to enhance collaboration shall be created. Samples of different matrices shall be exchanged to harmonize the chemical analysis and establish interlaboratory comparisons. Such activities might be facilitated by joining international associations or organizations, where researchers can offer their expertise, or by forming a new pesticide network for Central and South America that could present tailored projects to national and international organizations and funding agencies.

Pesticides in Agricultural Soils: Major Findings from Various Monitoring Campaigns in Switzerland.

Synthetic pesticides are widely applied in modern agriculture, where they are used against diseases, pests, and weeds to secure crop yield and quality. However, their intensive application has led to widespread contamination of the environment, including soils. Due to their inherent toxicity, they might pose a risk to soil health by causing harm to non-target organisms and disrupting ecosystem services in both agricultural and other exposed soils. Following the Swiss National Action Plan on the reduction of pesticide risks, Agroscope has conducted several soil monitoring studies that are briefly presented here. All of them resort to different multi-residue trace analytical approaches to simultaneously quantify up to about 150 modern pesticides by either accelerated solvent, or Quick, Easy, Cheap, Efficient, Rugged, Safe (QuEChERS) extraction, followed by separation and detection with liquid chromatography-triple quadrupole mass spectrometry. While partly still in progress, our investigations led to the following major findings this far: Multiple pesticides are commonly present in soils, with individual concentrations in agricultural soils often reaching up to a few tens of µg/kg. Pesticide occurrence and concentrations in agricultural soils primarily depend on land use, land use history and cultivated crops. Pesticides can prevail much longer than predicted by their half-lives, and were found in soils even decades after conversion from conventional to organic farming. Corresponding residual fractions can be in the order of a few percent of the originally applied amounts. We further found negative associations of pesticide residues with the abundance of beneficial soil life, underpinning their potential risk to the fertility of agricultural soils. Traces of pesticides are also detected in soils to which they were never applied, indicating contamination, e.g., via spray drift or atmospheric deposition. These results confirm the general notion of both scientists and legislators that prospective risk assessments (RA; as executed during registration and use authorization) should be confirmed and adjusted by retrospective RA (e.g., by environmental monitoring studies of currently used compounds) to jointly lead to an overall reduced environmental risk of pesticides.

Current analytical methods to quantify PAHs in activated carbon and vegetable carbon (E153) are not fit for purpose.

Pyrogenic carbonaceous materials (PCM) are increasingly used in a wide variety of consumer products, ranging from medicine, personal care products, food and feed additives, as well as drinking water purification. Depending on the product category and corresponding legislation, several terms are commonly used for PCM, such as Carbo activatus, C. medicinalis, vegetable carbon (E153), (activated) charcoal, (activated) biochar, or activated carbon. All PCM contain polycyclic aromatic hydrocarbons (PAHs) co-produced during pyrolysis. However, the actual PAH-content of PCM may range from negligibly low to alarmingly high depending on pyrolysis conditions and, if any, subsequent activation. Because of their health risk, PAHs need to be determined in many such PCM containing products, and concentrations are regulated by respective legally binding documents. Several such documents even specify the analytical method to be used. In this paper, we first argue that based on existing literature, currently legally binding methods to quantify PAHs in such products might not be fit for purpose. Secondly, we exemplarily determined PAH concentrations with a method previously optimized for biochar in a selection of 15 PCM or PCM-containing commercial products, illustrating that concentrations up to 30 mg kg-1 can be found. Consumer safety is of concern according to Swiss norms for drinking water and EU regulations for food additives for some of the investigated samples. In fact, some products would not have been allowed to be put on the market, if regulations with fit for purpose analytical methods existed. As PAHs were detected in considerable concentrations when extracted with toluene for 36 h, the authors suggest a corresponding adaption of existing methods and harmonization of the legislation.

Composition of PAHs in Biochar and Implications for Biochar Production.

The content of polycyclic aromatic hydrocarbons (PAHs) in biochar has been studied extensively; however, the links between biomass feedstock, production process parameters, and the speciation of PAHs in biochar are understudied. Such an understanding is crucial, as the health effects of individual PAHs vary greatly. Naphthalene (NAP) is the least toxic of the 16 US EPA PAHs but comprises the highest proportion of PAHs in biochar. Therefore, we investigate which parameters favor high levels of non-NAP PAHs (∑16 US EPA PAHs without NAP) in a set of 73 biochars. On average, the content of non-NAP PAHs was 9 ± 29 mg kg-1 (median 0.9 mg kg-1). Importantly, during the production of the biochars with the highest non-NAP PAH contents, the conditions in the post-pyrolysis area, where pyrolysis vapors and biochar are separated, favored condensation and deposition of PAHs on biochar. Under these conditions, NAP condensed to a lower degree because of its high vapor pressure. In biochars not contaminated through this process, the average non-NAP content was only 2 ± 3 mg kg-1 (median 0.5 mg kg-1). Uneven heat distribution and vapor trapping during pyrolysis and cool zones in the post-pyrolysis area need to be avoided. This demonstrates that the most important factor yielding high contents of toxic PAHs in biochar was neither a specific pyrolysis parameter nor the feedstock but the pyrolysis unit design, which can be modified to produce clean and safe biochar.

Heavy metals in soils of Mayabeque, Cuba: multifaceted and hardly discernable contributions from pedogenic and anthropogenic sources.

Cuba is a country with considerable potential for economic growth, and special efforts are made to increase the agricultural output. As food production depends on the quality of soils, heavy metal concentrations were measured in 39 soils in the province of Mayabeque, Cuba, and interpreted in light of anthropogenic activities and pedogenic conditions (soil type and properties). With median concentrations of 1.8 Cd, 60.3 Cr, 48.1 Cu, 36.2 Ni, 16.7 Pb, 55.0 Zn, and 0.1 mg/kg Hg, soils of Mayabeque were mostly below Cuban quality reference values (QRV) representing benchmarks of quality standards but no official threshold values. Only Cd concentrations were in many cases above the QRV of 0.6 mg/kg and some Cu concentrations above the one of 83 mg/kg. While Cd, Cr, and Ni concentrations were rather pedogenically driven, Cu, Pb, Zn, and Hg contents were rather anthropogenically influenced. When evaluated statistically, Cd and Cr showed most times a significant influence of both sources. In contrast, Ni and Zn could not be significantly related with the origins investigated in this study. Hence, the allocation of heavy metal concentrations to pedogenic or anthropogenic contamination or pollution sources is tentative and needs further investigations. Nevertheless, the present data adds information on soil heavy metal concentrations in the Caribbean region, serves as reference before further industrial development, and sets the ground for adaptation of the QRV for Cd and possibly future national environmental standards.

Choosing the best for preventing the worst: A structured analysis of the selection of risk management options in REACH restriction dossiers.

Under the European chemicals legislation REACH (Registration, Evaluation, Authorisation and restriction of CHemicals), the use of chemicals posing an unacceptable risk for humans and the environment can be restricted. This requires that regulatory authorities of EU member states, or the European Chemicals Agency on request of the Commission, submit a restriction proposal in which they suggest one or multiple risk management options (RMOs). The options are recommended to be evaluated in a socio-economic analysis (SEA) using defined criteria. This paper explores the drivers of the selection of the preferred RMO in 32 restriction dossiers. Applying principal component analysis reveals that the selection of the preferred RMO, and the evaluation of possible trade-offs between alternative RMOs, is determined by criteria characterizing a measure's effectiveness and practicality, in particular its risk reduction capacity (R) and proportionality. A logistic regression using quantitative estimates provided in SEA suggests that the probability for an RMO to be selected is the higher the higher its R and the lower the costs of the restriction. Based on our analysis we conclude that the selection process of RMOs in REACH restriction dossiers could be strengthened by defining a limited but unambiguous set of criteria, conducting a score-based evaluation as a default, and by defining transparent decision rules.

Socio-economic analysis in REACH restriction dossiers for chemicals management: A critical review.

This paper offers a critical review of socio-economic analysis (SEA) in Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) restriction dossiers. We examine the conceptual setup of SEA and identify the methods used for impact assessment. Moreover, we analyse the outcomes of quantitative impact assessment across restriction dossiers and substance groups. We find that impact assessment has largely focused on economic and health impacts. Environmental, social, wider economic and distributional impacts have either been evaluated qualitatively or not at all. While this can be explained by the specific scope of the proposed restriction or by lacking data, we also observe a lack of approaches for environmental and health impact assessment. This underlines the need to develop integrated methods that transform information about chemical effects and risks into impacts and, ultimately, into benefits and damages. Furthermore, to strengthen the function of SEA as decision-support tool in REACH restriction procedures, a comparative SEA of at least two alternative restriction options should be the default.

Desorption Resistance of Polycyclic Aromatic Hydrocarbons in Biochars Incubated in Cow Ruminal Liquid in Vitro and in Vivo.

Biochar is a new, promising, and sustainable feed additive alternative in agricultural production, which may, however, contain a considerable amount of polycyclic aromatic hydrocarbons (PAHs). As a measure of their bioaccessibility to ruminants, we quantified PAH concentrations in biochars before and after three different incubation experiments. Specifically, the biochars were subjected to (1) an aqueous cyclodextrin suspension with a contaminant trap as (infinite) sink, (2) an in vitro experiment with cow ruminal liquid and a contaminant trap, and (3) an in vivo experiment within cow rumen. Three different biochars were used that contained 13-407 mg/kgdw of the sum of 16 U.S. EPA PAHs before the exposure. While experiment (1) resulted in no or minimal bioaccessibility (desorption resistance) of the PAHs expressed by their largely unaltered concentrations, experiments (2) and (3) caused concentration reductions on average by 35 and 56%, respectively, presumably mainly due to the presence of the ruminal fluid in (2) and (3), and the extended sorption capacity in (3). Thus, simple and "abiotic" passive sampling methods may not capture all processes contributing to bioaccessibility in complex biological systems. A comparison with average daily PAH intake of ruminants suggests that quality-controlled biochar containing <10 mg/kgdw PAHs will not pose an increased risk when applied as a feed additive.

Designing biochar properties through the blending of biomass feedstock with metals: Impact on oxyanions adsorption behavior.

Metal-blending of biomass prior to pyrolysis is investigated in this work as a tool to modify biochar physico-chemical properties and its behavior as adsorbent. Six different compounds were used for metal-blending: AlCl3, Cu(OH)2, FeSO4, KCl, MgCl2 and Mg(OH)2. Pyrolysis experiments were performed at 400 and 700 °C and the characterization of biochar properties included: elemental composition, thermal stability, surface area and pore size distribution, Zeta potential, redox potential, chemical structure (with nuclear magnetic resonance) and adsorption behavior of arsenate, phosphate and nitrate. Metalblending strongly affected biochars' surface charge and redox potential. Moreover, it increased biochars' microporosity (per mass of organic carbon). For most biochars, mesoporosity was also increased. The adsorption behavior was enhanced for all metal-blended biochars, although with significant differences across species: Mg(OH)2-blended biochar produced at 400 °C showed the highest phosphate adsorption capacity (Langmuir Qmax approx. 250 mg g-1), while AlCl3-blended biochar produced also at 400 °C showed the highest arsenate adsorption (Langmuir Qmax approx. 14 mg g-1). Significant differences were present, even for the same biochar, with respect to the investigated oxyanions. This indicates that biochar properties need to be optimized for each application, but also that this optimization can be achieved with tools such as metal-blending. These results constitute a significant contribution towards the production of designer biochars.

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.

Effect of ageing on the properties and polycyclic aromatic hydrocarbon composition of biochar.

The influence of ageing on biochar properties has been investigated by comparing three fresh biochars with biochars artificially aged by either H2O2 thermal oxidation or horseradish peroxidase enzymatic oxidation. In addition, a field-aged counterpart for one of the biochars was recovered from an agricultural field site, four years after application. Biochar properties, including surface areas and pore volumes (derived by N2 and CO2 physisorption) and elemental compositions, showed only minor changes following both artificial and field ageing, indicating high biochar stability. Concentrations of the 16 US EPA PAHs were measured in all of the biochars and a contaminant trap was used to investigate the effect of ageing on their bioaccessibility. The concentrations of total and bioaccessible PAHs ranged from 4.4 to 22.6 mg kg-1 and 0.0 to 9.7 mg kg-1, respectively. Concentrations of the 16 US EPA PAHs decreased following field ageing, but the proportion of low molecular weight PAHs increased. The observed changes in PAH composition with field ageing can be explained by uptake from the surrounding soil and intra-biochar transfer processes. To better understand changes in PAH composition with ageing, an additional broad range of alkylated PAHs was also analyzed in selected samples. Our results show that the tested artificial ageing protocols are unable to approximate the changes in PAH composition resulting from field ageing. Nevertheless, total and bioaccessible PAH concentrations decreased for both artificially and field-aged biochars, indicating that biochars release PAHs when they are freshly produced and that the risk of PAH release decreases with ageing.

Polycyclic aromatic hydrocarbons and polychlorinated biphenyls in soils of Mayabeque, Cuba.

Cuba is a country in transition with a considerable potential for economic growth. Soils are recipients and integrators of chemical pollution, a frequent negative side effect of increasing industrial activities. Therefore, we established a soil monitoring network to monitor polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in soils of Mayabeque, a Cuban province southeast of Havana. Concentrations of the sum of the 16 US EPA PAHs and of the seven IRMM PCBs in soils from 39 locations ranged from 20 to 106 µg kg-1 and from 1.1 to 7.6 µg kg-1, respectively. While such concentrations can be considered as low overall, they were in several cases correlated with the distance of sampling sites to presumed major emission sources, with some of the concomitantly investigated source diagnostic PAH ratios, and with black carbon content. The presented data adds to the limited information on soil pollution in the Caribbean region and serves as a reference time point before the onset of a possible further industrial development in Cuba. It also forms the basis to set up and adapt national environmental standards.

Bioavailability and bioaccessibility of polycyclic aromatic hydrocarbons from (post-pyrolytically treated) biochars.

Bioaccessibility data of PAHs from biochar produced under real world conditions is scarce and the influence of feedstock and various post-pyrolysis treatments common in agriculture, such as co-composting or lacto-fermentation to produce silage fodder, on their bioavailability and bioaccessibility has hardly been studied. The total (Ctotal), and freely dissolved (i.e., bioavailable) concentrations (Cfree) of the sum of 16 US EPA PAHs of 43 biochar samples produced and treated in such ways ranged from 0.4 to almost 2000 mg/kg, and from 12 to 81 ng/L, respectively, which resulted in very high biochar-water partition coefficients (4.2 ≤ log KD ≤ 8.8 L/kg) for individual PAHs. Thirty three samples were incubated in contaminant traps that combined a diffusive carrier and a sorptive sink. Incubations yielded samples only containing desorption-resistant PAHs (Cres). The desorption resistant PAH fraction was dominant, since only eight out of 33 biochar samples showed statistically significant bioaccessible fractions (fbioaccessible = 1 - Cres/Ctotal). Bioavailability correlated positively with Ctotal/surface area. Other relationships of bioavailability and -accessibility with the investigated post-pyrolysis processes or elemental composition could not be found. PAH exposure was very limited (low Cfree, high Cres) for all samples with low to moderate Ctotal, whereas higher exposure was determined in some biochars with Ctotal > 10 mg/kg.

Time matters: A stock-pollution approach to authorisation decision-making for PBT/vPvB chemicals under REACH.

A core aim of the European chemicals legislation REACH is to ensure that the risks caused by substances of very high concern (SVHC) are adequately controlled. Authorisation - i.e. the formal approval of certain uses of SVHC for a limited time - is a key regulatory instrument in order to achieve this goal. For SVHC which are, in addition to their toxicity, (very) persistent and/or (very) bioaccumulative (PBT/vPvB chemicals), decision-making on the authorisation is conditional on a socio-economic analysis (SEA). In a SEA companies must demonstrate that the gains from keeping a chemical in use outweigh expected damage costs for society. The current setup of the REACH authorisation process, including existing guidance on performing a SEA, ignores that PBT/vPvB chemicals are stock pollutants. This paper explores the implications of incorporating stock pollution effects of these chemicals into a SEA on authorisation decision-making. We develop a cost-benefit approach which includes stock dynamics of PBT/vPvB chemicals. This allows identifying the decision rules for granting or refusing an authorisation. Furthermore, we generalize the model to an entire set of damage functions. We show that ignoring stock pollution effects in a SEA may lead to erroneous decisions on the use of PBT/vPvB chemicals because long-term impacts are not adequately captured. Using a historic case of DDT soil contamination as an illustrative example we discuss information requirements and challenges for authorisation decisions on the use of PBT/vPvB chemicals under REACH.

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.

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.