Industrial byproducts for the soil stabilization of trace elements and per- and polyfluorinated alkyl substances (PFASs).

The present work was the first exploration of the use of industrial byproducts from iron and titanium processing as sorbents for the stabilization of soil contamination. The main aim was to test slag waste and iron-rich charred fossil coal ("Fe-char"), as sorbents for per- and polyfluorinated alkyl substances (PFASs), as well as lead (Pb) and antimony (Sb), in four soils from a firefighting training area (PFASs) and a shooting range (Pb and Sb). Adding slag (10-20%) to shooting range soils decreased the leaching of Pb and Sb up to 50-90%. Fe-char amendment to these soils resulted in a moderate reduction in Sb leaching (20-70%) and a slightly stronger effect on Pb (40-50%). The sorption is most likely explained by the presence of Fe oxyhydroxides. These are present in the highest concentrations in the slag, probably resulting in more effective metal binding to the slag than to the Fe-char. Fe-char but not slag proved to be a strong sorbent for PFASs (reducing PFAS leaching from the soil by up to 99.7%) in soil containing low total organic carbon (TOC; 1.2%) but not in high-TOC soil (34%). The sorption coefficient KD for Fe-char was high, in the range of 104.3 to 106.5 L/kg at 1 ng/L in the low-TOC soil. The KD value increased with increasing perfluorocarbon chain length, exceeding PFAS sorption to biochar in the low ng/L concentration range. This result indicates that the mechanism behind the strong PFAS sorption to Fe-char was mainly van der Waals dispersive interactions between the hydrophobic PFAS-chain and the aromatic π-electron systems on nanopore walls within the Fe-char matrix. Overall, this study indicates that industrial byproducts can provide sustainable and cost-effective materials for soil remediation. However, the sorbent needs to be tailored to the type of soil and type of contamination.

Synergistic Properties of Arabinogalactan (AG) and Hyaluronic Acid (HA) Sodium Salt Mixtures.

The properties of mixtures of two polysaccharides, arabinogalactan (AG) and hyaluronic acid (HA), were investigated in solution by the measurement of diffusion coefficients D of water protons by DOSY (Diffusion Ordered SpectroscopY), by the determination of viscosity and by the investigation of the affinity of a small molecule molecular probe versus AG/HA mixtures in the presence of bovine submaxillary mucin (BSM) by 1HNMR spectroscopy. Enhanced mucoadhesive properties, decreased mobility of water and decreased viscosity were observed at the increase of AG/HA ratio and of total concentration of AG. This unusual combination of properties can lead to more effective and long-lasting hydration of certain tissues (inflamed skin, dry eye corneal surface, etc.) and can be useful in the preparation of new formulations of cosmetics and of drug release systems, with the advantage of reducing the viscosity of the solutions.

Biochar from Pine Wood, Rice Husks and Iron-Eupatorium Shrubs for Remediation Applications: Surface Characterization and Experimental Tests for Trichloroethylene Removal.

Nowadays porous materials from organic waste, i.e., Biochar (BC), are receiving increased attention for environmental applications. This study adds information on three BCs that have undergone a number of studies in recent years. A Biochar from pine wood, one from rice husk and one from Eupatorium shrubs enriched with Iron, labelled as PWBC, RHBC and EuFeBC respectively, are evaluated for Trichloroethylene (TCE) removal from aqueous solution. Physical-chemical description is performed by SEM-EDS and BET analysis. The decrease of TCE over time follows a pseudo-second order kinetics with increased removal by the PWBC. Freundlich and Langmuir models well fit equilibrium test data. The optimized values of the maximum adsorbed amount, qmax (mg g-1), follows this order 109.41 PWBC > 30.35 EuFeBC > 21.00 RHBC. Fixed-bed columns are also carried out. Best performance is again achieved by PWBC, which operates for a higher number of pore volume, followed by EuFeBC and RHBC. Continuous testing confirms batch studies and makes it possible to evaluate the workability of materials in configurations closer to reality. Results are promising for potential environmental application. In particular, the characterization of several classes of contaminants opens the doors to possible uses in mixed contamination cases.

Stabilization of PFAS-contaminated soil with activated biochar.

Biochars are considered potential sustainable sorbents to reduce the leaching of per- and polyfluoroalkyl substances (PFAS) from contaminated soils. However, biochar characteristics must probably be optimized to achieve useful sorption capacity. In the present work, eight waste timber biochars were produced, including biochars activated to different degrees, at different temperatures, and using both steam and CO2. In laboratory batch experiments, the eight biochars were amended to soil samples from two different horizons, with low and high total organic carbon (TOC, 1.6% and 34.2%, respectively), of a heavily PFAS-contaminated soil (1200-3800 µg kg-1 PFAStot), at varying doses (0, 0.1, 0.5, 1.0 and 5.0%). With a 5% amendment to the low-TOC soil, all eight biochars resulted in strongly reduced leachate PFAS concentrations (by 98-100%). At the same amendment dose in the high-TOC soil, leachate concentration reductions were more modest (23-100%). This was likely due to a strong PFAS-sorption to the high-TOC soil itself, as well as biochar pore clogging in the presence of abundant organic matter, resulting in fewer sorption sites available to PFAS. Reduction in PFAS leaching was proportional to the degree of activation and activation temperature. Thus, lower amendment doses of activated biochars were needed to reduce PFAS leaching to the same level as with the non-activated biochar. Activation however, came at a tradeoff with biochar yield. Furthermore, the adsorption ability of these biochars increased proportionally with PFAS-fluorocarbon chain length, demonstrating the role of hydrophobic interactions in reduction of PFAS leaching. Development of internal surface area and porosity was proposed as the main factor causing the improved performance of activated biochars. This study shows that woody residues such as waste timber can be used to produce effective sorbents for the remediation of PFAS-contaminated soil. It also highlights the desirability of sorbate and matrix-specific optimization of biochar production.

Arabinogalactan and hyaluronic acid in ophthalmic solution: Experimental effect on xanthine oxidoreductase complex as key player in ocular inflammation (in vitro study).

Dry eye syndrome is a common disease associated to eyes inflammation, irritation and tear film instability. The enzymatic complex of xanthine oxidoreductase (XOR) is involved in the generation of reactive oxygen species (ROS) and uric acid that, in the end, can cause reperfusion injuries, irritation and pathological conditions. Furthermore, in the eye, it has been proposed that oxygen free radicals might play a significant role in retinal ischemic damage. A new artificial drop formulation based on arabinogalactan and hyaluronic acid has been proposed in this article. The uric acid and the ROS formation have been monitored. The effect of the arabinogalactan, the hyaluronic acid and their mixture has been studied. The arabinogalactan entails a uric acid and ROS reduction of 27% and 38% respectively; no significant reduction of uric acid or ROS has been observed after the addition of hyaluronic acid alone. Notably the combination of arabinogalactan and hyaluronic acid involves the reduction of uric acid and ROS equal to 38% and 62%, namely. This study demonstrates that this artificial drop formulation can markedly reduce the uric acid and ROS formation in vitro; thus, the use of this formulation may contribute in the resolution of the dry eye syndrome.

The effect of biochar, lime and ash on maize yield in a long-term field trial in a Ultisol in the humid tropics.

A multi-season field trial was carried out to investigate the effect of the amendment of biochar, lime, ash and washed biochar on the growth of maize. A degraded, strongly acidic Ultisol (pHKCl 3.60), with a relatively high exchangeable aluminium content (2.4 cmolc/kg) and a low exchangeable calcium content (0.99 cmolc/kg), was used. Soil was treated once at the beginning of the field trial and crop growth was monitored over seven planting seasons (PS). All treatments increased maize yield. The average increases were; seven times for biochar, five times for lime, five times for washed biochar and eight times for ash treatment, when compared to the control across all PS. The effect of biochar, lime and ash treatments on maize yield were sustained over the seven PS. Soil pHKCl was significantly increased (p < 0.05 level) following the addition of all of the amendment materials. All treatments significantly reduced the concentration of Al3+ when compared to the control (p < 0.05), with the lowest concentrations for the lime and ash treatments. The ash treatment also increased the concentration of macronutrients (K, P and Mg) to the greatest extent. Results showed that there was a clear liming effect at play. The better performance of biochar compared to lime, despite lime having the highest pH and the lowest Al3+ concentration, can be explained by the additional K, Mg and P the biochar adds to the soil. Results also showed a clear nutrient addition effect where ash added the most nutrients. Overall, this work supports the fact that small scale farmers in Indonesia should produce biochar from their waste agricultural materials. Doing so not only provides an increase in crop productivity, but also sequesters carbon resulting in the best overall environmental benefit.

Waste timber pyrolysis in a medium-scale unit: Emission budgets and biochar quality.

Pyrolysis of organic waste or woody materials yields a stable carbonaceous product that can be mixed into soil and is often termed "biochar". During pyrolysis carbon-containing gases are emitted, mainly volatile organic carbon species, carbon monoxide and aerosols. In modern pyrolysis units, gases are after-combusted, which reduces emissions substantially. However, emission data for medium- to large-scale pyrolysis units are scant, both regarding gases, aerosols, heavy metals and polycyclic aromatic hydrocarbons (PAH). Making biochar from lightly contaminated waste timber (WT) is a promising waste handling option as it results in the potential valorization of such residues into e.g. sorbents for contaminant stabilization. For this process to be environmentally sustainable, emissions during the process need to be low and the resulting biochar of sufficient quality. To investigate both issues, we pyrolyzed three batches of WT and one reference batch of clean wood/leaves in a representative medium-scale pyrolysis unit (Pyreg-500, 750 t/year) with after-combustion of the pyrolysis gases, and measured the gas, aerosol, metal and PAH emissions, as well as the characteristics and contamination levels of the resulting biochar, including contaminant leaching. Mean emission factors for the WT were (g/kg biochar); CO = 7 ±â€¯2, non-methane volatile organic compounds (NMVOC) = 0.86 ±â€¯0.14, CH4 = 0, aerosols (PM10) = 0.6 ±â€¯0.3, total products of incomplete combustion (PIC) = 9 ±â€¯3, PAH-16 = (2.0 ±â€¯0.2) ·â€¯10-5, As (most abundant metal) = (2.3 ±â€¯1.9) ·â€¯10-3 and NOX = 0.65 ±â€¯0.10. There were no significant differences in emission factors between the pyrolysis of WT and the reference respectively, except for PM10, NMVOC, and PAH-16, which were significantly lower for WT than for the clean wood/leaves. The WT biochar did not satisfy premium or basic European Biochar Certificate criteria due to high levels of zinc and PAH. However, leachable metal contents were <0.1% of total contents. Still, use of the WT-biochar without further improvement or investigation would be limited to ex situ use, not improving soil fertility or in situ remediation.

Can biochar and designer biochar be used to remediate per- and polyfluorinated alkyl substances (PFAS) and lead and antimony contaminated soils?

Designer biochars can be used to remediate organic and inorganic contaminant polluted soils. Here, a waste timber biochar (BC), a coconut shell activated biochar (aBC) and a wood shrub iron enriched designer biochar (Fe-BC) were investigated. Per- and polyfluorinated alkyl substances (PFAS) contaminated soils with different total organic carbon (TOC) contents (1.6 and 34.2%) were amended with six doses of BC and aBC. Two shooting range soils (TOC 5.2 and 10.2%) contaminated with heavy metals (mainly Pb and Sb) were amended with four doses of BC and Fe-BC. An amendment of 20% BC reduced the PFOS leachate concentration by 86% for the low TOC soil but was not effective for the high TOC soil. An amendment of 1% aBC reduced PFOS leachate concentrations by over >96% for both soils. For the low TOC shooting range soil, a 20% amendment of BC reduced Pb and Sb leaching by 61% and 12%, respectively. An amendment of 20% Fe-BC to soil with low TOC reduced Pb and Sb leaching by 99% and 40%, respectively. The need for "designer" biochars using processes such as iron enrichment or activation should be considered depending on the TOC of the soil, the type of contaminants and remediation goals.

Can polyethylene passive samplers predict polychlorinated biphenyls (PCBs) uptake by earthworms and turnips in a biochar amended soil?

A pot experiment was carried out in which aged polychlorinated biphenyls (PCBs) contaminated soil was amended with biochar, and three phases: earthworms, turnips and polyethylene (PE) passive samplers, were added simultaneously in order to investigate changes in bioavailability of PCB following biochar amendment. Two biochars were used: one made from rice husk in Indonesia using local techniques and the other made from mixed wood shavings using more advanced technology. The biochars were amended at 1 and 4% doses. The overall accumulation of PCBs to the phases followed the order: earthworm lipid > PE > turnip. The rice husk biochar reduced PCB accumulation to a greater degree than the mixed wood biochar for all phases, however there was no effect of dose for either biochar. Earthworm uptake was reduced between 52% and 91% for rice husk biochar and by 19% to 63% for mix wood biochar. Turnip uptake was not significantly reduced by biochar amendment. Phase to soil accumulation factors (PSAF) were around 0.5 for turnips, approximately 5 for PE and exceeded 100 for earthworms. This study demonstrates that both biochars can be a sustainable alternative for in situ soil remediation and that PE can be used as tool to simulate the uptake in earthworms and thus remediation effectiveness.

Sorption of α-, ß-, γ- and δ-hexachlorocyclohexane isomers to three widely different biochars: Sorption mechanisms and application.

Within this study different biochars (BC) with widely varying characteristics have been tested as materials for the adsorption of hexachlorocyclohexane's (HCH) isomers (α, ß, γ and δ) from water. Three BCs produced from digestate (700 °C), greenhouse tomato waste (550 °C) and durian shell (400 °C) were tested. The BCs demonstrated variable physico-chemical characteristics, especially with respect to surface area, with CO2-surface area ranging from 5.4 to 328.6 m2 g-1 and iron content ranging from 0.0733 to 11.17 g kg-1. Isotherm tests were carried out to understand which mechanisms drive HCH uptake to BC, to assess whether stereochemistry affects adsorption and to assess whether competitive sorption occurs. Log KF values ranged from 3.7 to 5.8 (µg kg-1) (µg L-1)-n for the various isomers on the three biochars. No competition (t-test, P < 0.0001) was observed between α-, ß-, γ- and δ-HCH. Freundlich adsorption constants of α-, γ- and δ-HCH followed the order: BC digestate > BC greenhouse tomato waste > BC durian shell, in contrast to ß-HCH which followed the order: BC durian shell > BC greenhouse tomato waste > BC digestate. In addition to stereochemistry, sorption coefficients were affected most strongly by BC surface area and iron content, in addition to specific HCH/BC matrix interactions. In this study the iron content of a carbonaceous material has been investigated, for the first time, as a factor that can affect the sorption of HCHs.

Fading positive effect of biochar on crop yield and soil acidity during five growth seasons in an Indonesian Ultisol.

Low fertility limits crop production on acidic soils dominating much of the humid tropics. Biochar may be used as a soil enhancer, but little consensus exists on its effect on crop yield. Here we use a controlled, replicated and long-term field study in Sumatra, Indonesia, to investigate the longevity and mechanism of the effects of two contrasting biochars (produced from rice husk and cacao shell, and applied at dosages of 5 and 15tha-1) on maize production in a highly acidic Ultisol (pHKCl3.6). Compared to rice husk biochar, cacao shell biochar exhibited a higher pH (9.8 vs. 8.4), CEC (197 vs. 20cmolckg-1) and acid neutralizing capacity (217 vs. 45cmolckg-1) and thus had a greater liming potential. Crop yield effects of cacao shell biochar (15tha-1) were also much stronger than those of rice husk biochar, and could be related to more favorable Ca/Al ratios in response to cacao shell biochar (1.0 to 1.5) compared to rice husk biochar (0.3 to 0.6) and nonamended plots (0.15 to 0.6). The maize yield obtained with the cacao shell biochar peaked in season 2, continued to have a good effect in seasons 3-4, and faded in season 5. The yield effect of the rice husk biochar was less pronounced and already faded from season 2 onwards. Crop yields were correlated with the pH-related parameters Ca/Al ratio, base saturation and exchangeable K. The positive effects of cocoa shell biochar on crop yield in this Ultisol were at least in part related to alleviation of soil acidity. The fading effectiveness after multiple growth seasons, possibly due to leaching of the biochar-associated alkalinity, indicates that 15tha-1 of cocoa shell biochar needs to be applied approximately every third season in order to maintain positive effects on yield.

Monitoring alkylphenols in water using the polar organic chemical integrative sampler (POCIS): Determining sampling rates via the extraction of PES membranes and Oasis beads.

Polar organic chemical integrative samplers (POCIS) have previously been used to monitor alkylphenol (AP) contamination in water and produced water. However, only the sorbent receiving phase of the POCIS (Oasis beads) is traditionally analyzed, thus limiting the use of POCIS for monitoring a range of APs with varying hydrophobicity. Here a "pharmaceutical" POCIS was calibrated in the laboratory using a static renewal setup for APs (from 2-ethylphenol to 4-n-nonylphenol) with varying hydrophobicity (log Kow between 2.47 and 5.76). The POCIS sampler was calibrated over its 28 day integrative regime and sampling rates (Rs) were determined. Uptake was shown to be a function of AP hydrophobicity where compounds with log Kow < 4 were preferentially accumulated in Oasis beads, and compounds with log Kow > 5 were preferentially accumulated in the PES membranes. A lag phase (over a 24 h period) before uptake in to the PES membranes occurred was evident. This work demonstrates that the analysis of both POCIS phases is vital in order to correctly determine environmentally relevant concentrations owing to the fact that for APs with log Kow ≤ 4 uptake, to the PES membranes and the Oasis beads, involves different processes compared to APs with log Kow ≥ 4. The extraction of both the POCIS matrices is thus recommended in order to assess the concentration of hydrophobic APs (log Kow ≥ 4), as well as hydrophilic APs, most effectively.

Characterizing Biochar as Alternative Sorbent for Oil Spill Remediation.

Biochar (BC) was characterized as a new carbonaceous material for the adsorption of toluene from water. The tested BC was produced from pine wood gasification, and its sorption ability was compared with that of more common carbonaceous materials such as activated carbon (AC). Both materials were characterized in terms of textural features and sorption abilities by kinetic and equilibrium tests. AC and BC showed high toluene removal from water. Kinetic tests demonstrated that BC is characterized by faster toluene removal than AC is. Textural features demonstrated that the porosity of AC is double that of BC. Nevertheless, equilibrium tests demonstrated that the sorption ability of BC is comparable with that of AC, so the materials' porosity is not the only parameter that drives toluene adsorption. The specific adsorption ability (mg sorbed m-2 of surface) of the BC is higher than that of AC: toluene is more highly sorbed onto the biochar surface. Biochar is furthermore obtained from biomaterial thermally treated for making energy; this also makes the use of BC economically and environmentally convenient compared with AC, which, as a manufactured material, must be obtained in selected conditions for this type of application.