Metal sorption by biochars: A trade-off between phosphate and carbonate concentration as governed by pyrolysis conditions.

Three feedstocks, pine wood, grass and cow manure, were pyrolyzed under various conditions and tested on their ability to sorb metals in aquatic systems. The feedstocks were pyrolyzed at 2 different temperatures (350 °C and 550 °C) and 2 different residence times (10 and 60 min) and resulting biochars were assessed on their capability to immobilize Pb, Cu, Cd and Zn. Manure-based chars, and to a lesser extent grass-based chars, featured high concentrations of phosphates and carbonates. These anions play an important role in metal sorption because they form insoluble complexes with the metals. Washing reduced the concentration of these anions, leading to a reduced sorption of metals by the biochar. The carbonate concentration on the biochars' surface increased at higher reactor temperature and longer residence times. The opposite trend was observed for the phosphate concentration and the cation exchange capacity. Accordingly, the optimal temperature-residence time combination for sorption was a trade-off between these properties. Biochar produced from cow manure and pyrolyzed at 550 °C for 10 min showed the best sorption for all metals considered.

Establishment of optimal barley straw biochar application conditions for rice cultivation in a paddy field.

This study was conducted to establish the optimal application conditions of barley straw biochar (BC) for rice cultivation and to determine the effects of combined application of BC and inorganic fertilizer (IF) on rice cultivation in a paddy field. Based on the characteristics of rice growth in pot-based experiments, the selected optimal application conditions of BC were application of 20 ton ha-1 at 14 days before rice transplanting. The effects of BC application on rice cultivation in a paddy field when using those conditions were then evaluated. Each treatment was separated by a control (Cn), IF, BC, and combined BC + IF treatments, respectively. The rice yields in the BC + IF treatment were 38.6, 21.7, and 24.5% greater than those in the Cn, IF, and BC treatments, respectively. In addition, yield components of rice were significantly improved in the BC + IF treatment relative to the other treatments. Following rice harvest, soil status was improved, showing greater soil aggregation stability, decreased bulk density, and increased porosity in the BC-treated areas compared to those in the Cn- and IF-treated areas. At the time of rice harvesting, soil chemical properties such as pH, EC, SOC, TN, Avail. P2O5, and CEC in the BC-treated areas were improved over those in other areas. The results of this study indicate that using BC as a soil amendment is effective at improving rice cultivation and can benefit the soil environment.

Biochar-mediated sorption of antibiotics in pig manure.

Using manure contaminated with antibiotics as fertilizer is a primary source of soil pollution with antibiotics and concomitantly with antibiotic resistance genes (ARG). Bioavailable antibiotics trigger further ARG amplification during manure storage. Consequently it is aimed to facilitate the immobilization of antibiotics in manure. To this end, five biochars derived from pine cone (BCP), rice husk, sewage sludge, digestate and Miscanthus were tested as additional sorbents in liquid pig manure for sulfamethazine, ciprofloxacin, oxytetracycline and florfenicol. Non-linear sorption was best-fit using the Freundlich isotherm (R2 > 0.82) and the pseudo-second-order model best described sorption kinetics (R2 > 0.94). Antibiotics' sorption onto manure increased in the order sulfamethazine < florfenicol < ciprofloxacin < oxytetracycline. Admixtures of BCP to manure changed the order to sulfamethazine < oxytetracycline < florfenicol = ciprofloxacin. Generally, with the addition of biochar, sorption coefficients of florfenicol increased most (by factors>2.7) followed by sulfamethazine and ciprofloxacin. Yet, oxytetracycline was mostly mobilized probably due to competitive adsorption. Effects depended on the proportion of biochar added and the type of biochar, whereby plant-derived biochar exhibited better immobilization of antibiotics. Depending on the type and portion of biochar, admixtures to manure can be used to lower the mobility and hence bioavailability of fenicols, fluoroquinolones and sulfonamides.

Impact of organic amendments (biochar, compost and peat) on Cd and Zn mobility and solubility in contaminated soil of the Campine region after three years.

To determine the long-term impact of organic amendments on metal (Cd and Zn) immobilization, soil from the Campine region was amended with holm oak-derived biochar, compost, and peat, and monitored over a 3-year period. Pot experiments were conducted by mixing the amendments independently at 2% and 4% (g/g) with the soil. The mobility and solubility of metals in the treatments were assessed by means of rhizon soil moisture samplers, sequential BCR extractions, and diffusive gradient in thin films (DGT). Over the three-year period, the 2% biochar addition resulted in an average decrease in pore water concentration of 40% for Cd and 48% for Zn whereas the 4% addition led to an average decrease of 66% for Cd and 77% for Zn. The immobilization effect in the biochar treatments was attributed to the consistently higher pH and lower concentrations of dissolved organic carbon (DOC) in the soil. The latter may have been caused by sorption of DOC onto the surface of biochar thereby increasing its negatively charged functional groups that are able to sorb cations. On the other hand, compost and peat had the unwanted effect of significantly increasing the concentrations of Cd and Zn in the soil pore water. This was partly due to the formation of soluble organo-metallic complexes as significantly higher DOC concentrations were found in the compost and peat treatments. Results from the DGT measurements, after a 24 h deployment time, revealed a low resupply (R ≤ 0.4) of Cd and Zn from the solid phase to the soil solution in both amended and unamended soil. This suggests a case of slow metal desorption kinetics in the soil that was relatively unchanged by the presence of organic amendments.

Limitations for phytoextraction management on metal-polluted soils with poplar short rotation coppice-evidence from a 6-year field trial.

Poplar clones were studied for their phytoextraction capacity in the second growth cycle (6-year growth) on a site in the Belgian Campine region, which is contaminated with Cd and Zn via historic atmospheric deposition of nearby zinc smelter activities. The field trial revealed regrowth problems for some clones that could not be predicted in the first growth cycle. Four allometric relations were assessed for their capacity to predict biomass yield in the second growth cycle. A power function based on the shoot diameter best estimates the biomass production of poplar with R2 values between 0.94 and 0.98. The woody biomass yield ranged from 2.1 to 4.8 ton woody Dry Mass (DM) ha-1 y-1. The primary goal was to reduce soil concentrations of metals caused by phytoextraction. Nevertheless, increased metal concentrations were determined in the topsoil. This increase can partially be explained by the input of metals from deeper soil layers in the top soil through litterfall. The phytoextraction option with poplar short rotation coppice in this setup did not lead to the intended soil remediation in a reasonable time span. Therefore, harvest of the leaf biomass is put forward as a crucial part of the strategy for soil remediation through Cd/Zn phytoextraction.

Potential value of phosphate compounds in enhancing immobilization and reducing bioavailability of mixed heavy metal contaminants in shooting range soil.

Shooting range soils contain mixed heavy metal contaminants including lead (Pb), cadmium (Cd), and zinc (Zn). Phosphate (P) compounds have been used to immobilize these metals, particularly Pb, thereby reducing their bioavailability. However, research on immobilization of Pb's co-contaminants showed the relative importance of soluble and insoluble P compounds, which is critical in evaluating the overall success of in situ stabilization practice in the sustainable remediation of mixed heavy metal contaminated soils. Soluble synthetic P fertilizer (diammonium phosphate; DAP) and reactive (Sechura; SPR) and unreactive (Christmas Island; CPR) natural phosphate rocks (PR) were tested for Cd, Pb and Zn immobilization and later their mobility and bioavailability in a shooting range soil. The addition of P compounds resulted in the immobilization of Cd, Pb and Zn by 1.56-76.2%, 3.21-83.56%, and 2.31-74.6%, respectively. The reactive SPR significantly reduced Cd, Pb and Zn leaching while soluble DAP increased their leachate concentrations. The SPR reduced the bioaccumulation of Cd, Pb and Zn in earthworms by 7.13-23.4% and 14.3-54.6% in comparison with earthworms in the DAP and control treatment, respectively. Bioaccessible Cd, Pb and Zn concentrations as determined using a simplified bioaccessibility extraction test showed higher long-term stability of P-immobilized Pb and Zn than Cd. The differential effect of P-induced immobilization between P compounds and metals is due to the variation in the solubility characteristics of P compounds and nature of metal phosphate compounds formed. Therefore, Pb and Zn immobilization by P compounds is an effective long-term remediation strategy for mixed heavy metal contaminated soils.

Comparative analysis of speciation and bioaccessibility of arsenic in rice grains and complementary medicines.

In many countries, rice grains and complementary medicines are important sources of arsenic (As) consumption. The objective of this study was to compare the speciation and bioaccessibility of As in selected rice grains and complementary medicines. A number of rice grain samples, and a range of herbal and ayurvedic medicines were analyzed for total As, speciation of As using sequential fractionation and extended x-ray absorption fine structure (EXAFS) techniques, and bioaccessibility of As using an in vitro extraction test. The daily intake of As through the uptake of these As sources was compared with the safety guidelines for As. The results demonstrated higher levels of As in ayurvedic medicines compared to herbal medicines and rice grains. The sequential fractionation showed the dominance of organic-bound As species in rice grains and herbal medicines, however, inorganic-bound As species dominated the ayurvedic medicines. This implies that As is derived from plant uptake in herbal medicines and rice grains, and from inorganic mineral input in ayurvedic medicines. Arsenic bioaccessibility was higher in ayurvedic than herbal medicines and rice grains, suggesting that inorganic As added as a mineral therapeutic input is more bioaccessible than organic As species derived from plant uptake. This study also showed a positive relationship between soluble As fractions and bioaccessibility indicating that solubility is an important factor controlling bioaccessibility. The daily intake values for As as estimated by total As content are likely to exceed the safe threshold level in rice grains that are enriched with As.

Mild hydrothermal conditioning prior to torrefaction and slow pyrolysis of low-value biomass.

The aim of this research was to establish whether hydrothermal conditioning and subsequent thermochemical processing via batch torrefaction or slow pyrolysis may improve the fuel quality of grass residues. A comparison in terms of fuel quality was made of the direct thermochemical processing of the feedstock versus hydrothermal conditioning as a pretreatment prior to thermochemical processing. Hydrothermal conditioning reduced ash content, and particularly nitrogen, potassium and chlorine contents in the biomass. The removal of volatile organic matter associated with thermochemical processes can increase the HHV to levels of volatile bituminous coal. However, slow pyrolysis only increased the HHV of biomass provided a low ash content (<6%) feedstock was used. In conclusion, hydrothermal conditioning can have a highly positive influence on the efficiency of thermochemical processes for upgrading low-value (high-ash) biomass to a higher quality fuel.

Speciation and bioavailability of lead in complementary medicines.

Complementary medicines have associated risks which include toxic heavy metal(loid) and pesticide contamination. The objective of this study was to examine the speciation and bioavailability of lead (Pb) in selected complementary medicines. Six herbal and six ayurvedic medicines were analysed for: (i) total heavy metal(loid) contents including arsenic (As), cadmium (Cd), Pb and mercury (Hg); (ii) speciation of Pb using sequential fractionation and extended x-ray absorption fine structure (EXAFS) techniques; and (iii) bioavailability of Pb using a physiologically-based in vitro extraction test (PBET). The daily intake of Pb through the uptake of these medicines was compared with the safety guidelines for Pb. The results indicated that generally ayurvedic medicines contained higher levels of heavy metal(loid)s than herbal medicines with the amount of Pb much higher than the other metal(loid)s. Sequential fractionation indicated that while organic-bound Pb species dominated the herbal medicines, inorganic-bound Pb species dominated the ayurvedic medicines. EXAFS data indicated the presence of various Pb species in ayurvedic medicines. This implies that Pb is derived from plant uptake and inorganic mineral input in herbal and ayurvedic medicines, respectively. Bioavailability of Pb was higher in ayurvedic than herbal medicines, indicating that Pb added as a mineral therapeutic input is more bioavailable than that derived from plant uptake. There was a positive relationship between soluble Pb fraction and bioavailability indicating that solubility is an important factor controlling bioavailability. The daily intake values for Pb as estimated by total and bioavailable metal(loid) contents are likely to exceed the safe threshold level in certain ayurvedic medicines. This research demonstrated that Pb toxicity is likely to result from the regular intake of these medicines which requires further investigation.

Evaluation of phosphorus adsorption capacity of sesame straw biochar on aqueous solution: influence of activation methods and pyrolysis temperatures.

The phosphorus (P) adsorption characteristic of sesame straw biochar prepared with different activation agents and pyrolysis temperatures was evaluated. Between 0.109 and 0.300 mg L(-1) in the form of inorganic phosphate was released from raw sesame straw biochar in the first 1 h. The release of phosphate was significantly enhanced from 62.6 to 168.2 mg g(-1) as the pyrolysis temperature increased. Therefore, sesame straw biochar cannot be used as an adsorbent for P removal without change in the physicochemical characteristics. To increase the P adsorption of biochar in aqueous solution, various activation agents and pyrolysis temperatures were applied. The amount of P adsorbed from aqueous solution by biochar activated using different activation agents appeared in the order ZnCl2 (9.675 mg g(-1)) > MgO (8.669 mg g(-1)) ⋙ 0.1N-HCl > 0.1N-H2SO4 > K2SO4 ≥ KOH ≥ 0.1N-H3PO4, showing ZnCl2 to be the optimum activation agent. Higher P was adsorbed by the biochar activated using ZnCl2 under different pyrolysis temperatures in the order 600 °C > 500 °C > 400 °C > 300 °C. Finally, the amount of adsorbed P by activated biochar at different ratios of biochar to ZnCl2 appeared in the order 1:3 ≒ 1:1 > 3:1. As a result, the optimum ratio of biochar to ZnCl2 and pyrolysis temperature were found to be 1:1 and 600 °C for P adsorption, respectively. The maximum P adsorption capacity by activated biochar using ZnCl2 (15,460 mg kg(-1)) was higher than that of typical biochar, as determined by the Langmuir adsorption isotherm. Therefore, the ZnCl2 activation of sesame straw biochar was suitable for the preparation of activated biochar for P adsorption.

Decline in extractable antibiotics in manure-based composts during composting.

A wide variety of antibiotics have been detected in natural water samples and this is of potential concern because of the adverse environmental effects of such antibiotic residues. One of the main sources of antibiotics effluence to the surrounding environment is livestock manures which often contain elevated concentrations of veterinary antibiotics (VAs) which survive digestion in the animal stomach following application in animal husbandry practices. In Korea, livestock manures are normally used for compost production indicating that there is potential for antibiotic release to the environment through compost application to agricultural lands. Therefore, reduction of the amount of VAs in composts is crucial. The purpose of this study was to understand the influence of the composting process and the components of the compost on the levels of three common classes of antibiotics (tetracyclines, sulfonamides, and macrolides). Composted materials at different stages of composting were collected from compost manufacturing plants and the variation in antibiotic concentrations was determined. Three different antibiotics, chlortetracycline (CTC), sulfamethazine (SMZ), and tylosin (TYL) at three different concentrations (2, 10, and 20mgkg(-1)) were also applied to a mixture of pig manure and sawdust and the mixtures incubated using a laboratory scale composting apparatus to monitor the changes in antibiotic concentrations during composting together with the physicochemical properties of the composts. During composting, in both field and lab-scale investigations, the concentrations of all three different antibiotics declined below the relevant Korean guideline values (0.8mgkg(-1) for tetracyclines, 0.2mgkg(-1) for sulfonamides and 1.0mgkg(-1) for macrolides). The decline of tetracycline and sulfonamide concentrations was highly dependent on the presence of sawdust while there was no influence of sawdust on TYL decline.

Applicability of the Charm II system for monitoring antibiotic residues in manure-based composts.

The effluence of veterinary antibiotics (VAs) to aquatic and terrestrial environments is of concern due to the potential adverse effects on human health, such as the production of antibiotic resistant bacteria. One of the main pathways for antibiotics to enter the environment is via the application of manure and/or manure-based composts as an alternative organic fertilizer to agricultural lands. While a wide diversity of manure-based composts are produced in Korea, there is currently no regulatory guideline for VA residues. Hence, monitoring and limiting the concentration of VA residues in manure and/or manure-based composts prior to application to the lands is important to mitigate any environmental burden. The current study was conducted to examine the applicability of the Charm II antibiotic test system for monitoring tetracyclines, sulfonamides and macrolides in manure-based composts. The Charm II system was a highly reproducible method for determining whether VA residue concentrations in manure-based compost exceeded specific guideline values. A wide range of manure-based composts and liquid fertilizers commercially available in Korea were examined using the Charm II system to monitor the residues of the target VAs. For this, the guideline concentrations of VA residues (0.8 mg kg(-1) for tetracyclines, 0.2 mg kg(-1) for sulfonamides, and 0.1 mg kg(-1) for macrolides) stated in 'Official Standard of Feeds' under the 'Control of Livestock and Fish Feed Act' in Korea were adopted to establish control points. Of the 70 compost samples examined 12 exceeded 0.8 mg kg(-1) for tetracyclines and 21 exceeded 0.2 mg kg(-1) for sulfonamides. Of the 25 liquid fertilizer samples examined most samples exceeded these prospective guidelines.

Mechanistic evidence and efficiency of the Cr(VI) reduction in water by different sources of zerovalent irons.

The objective of this research was to assess the mechanism and effectiveness of the zerovalent iron (ZVI) to remediate the Cr(VI) contaminated water. The mechanism of Cr(VI) reduction by ZVI was evaluated by characterising surface properties and chemical compositions of Fe and Cr products using SEM-EDS, XRD and XPS analyses. The effectiveness of ZVI in Cr(VI) reduction was assessed by the luminescent bacteria (Photobacterium Phosphoreum). The Cr(VI) was reduced to Cr(III), when the reactive Fe(o) was oxidised to Fe(II, III), showing the presence of Fe2O3, (Fe-Cr)2O3 and FeOOH. The SEM-EDS analysis showed that ZVI with a higher reducing capacity was more subject to changes of surface and morphological properties due to ionisation of ZVI. The Cr and Fe in precipitates subsisted exclusively in the Cr(III) or Fe(III) states with the respective forms of Cr(OH)3 or Cr2O3 and FeOOH or Fe2O3. Electrons produced from ZVI oxidation reduced Cr(VI) to Cr(III), thus resultantly Cr(III) precipitated or co-precipitated with Fe(III) to form Fe(III)-Cr(III) hydroxide or Fe(III)-Cr(III) oxyhydroxide. Toxicity of water reacted with ZVI was significantly lower than that of the untreated water.

Agricultural recycling of the by-product concentrate of livestock wastewater treatment plant processed with VSEP RO and bio-ceramic SBR.

One of the problems in a reverse osmosis process for livestock wastewater treatment is disposal of the by-product concentrate. The agricultural recycling of the concentrate is more cost saving than a further treatment. Application of the concentrate reduces the chemical fertilizer amendment. The agricultural recycling of the concentrate from the Kimhae livestock wastewater treatment plant, processed with the VSEP RO and bio-ceramic SBR, was studied. The concentrate includes non-biodegradable humic ubstance and residual inorganic ions (NH4+, NO3-, PO4(3-), K+, etc.). The contents of N, P and K were 1,650, 382 and 2,059 mg L(-1), respectively. The total acidity of humic acids extracted from the concentrate was 5.17 cmol(+) g(-1), composed of 2.38 cmol(+) g(-1) of carboxylic group and 2.79 cmol(+) g(-1) of phenolic hydroxyl group. Coliforms and E. coli were not detected in the concentrate. The yield of rice plant with the concentrate applied to it resulted in similar production to that with chemical fertilizer applied. The water extractable nitrate content of the concentrate-applied land did not exceed that of chemical fertilizer applied, at soil depths of 30 and 60 cm. The percolated amount of nitrate into the water table in arable land with the concentrate applied showed a similar level to that treated with the chemical fertilizer.