Stabilisation of soil organic matter with rock dust partially counteracted by plants.

Soil application of Ca- and Mg-rich silicates can capture and store atmospheric carbon dioxide as inorganic carbon but could also have the potential to stabilise soil organic matter (SOM). Synergies between these two processes have not been investigated. Here, we apply finely ground silicate rock mining residues (basalt and granite blend) to a loamy sand in a pot trial at a rate of 4% (equivalent to 50 t ha-1 ) and investigate the effects of a wheat plant and two watering regimes on soil carbon sequestration over the course of 6 months. Rock dust addition increased soil pH, electric conductivity, inorganic carbon content and soil-exchangeable Ca and Mg contents, as expected for weathering. However, it decreased exchangeable levels of micronutrients Mn and Zn, likely related to the elevated soil pH. Importantly, it increased mineral-associated organic matter by 22% due to the supply of secondary minerals and associated sites for SOM sorption. Additionally, in the nonplanted treatments, rock supply of Ca and Mg increased soil microaggregation that subsequently stabilised labile particulate organic matter as organic matter occluded in aggregates by 46%. Plants, however, reduced soil-exchangeable Mg and Ca contents and hence counteracted the silicate rock effect on microaggregates and carbon within. We suggest this cation loss might be attributed to plant exudates released to solubilise micronutrients and hence neutralise plant deficiencies. The effect of enhanced silicate rock weathering on SOM stabilisation could substantially boost its carbon sequestration potential.

The status of phosphorus levels in Iranian agricultural soils - a systematic review and meta-analysis.

Phosphorus (P) inputs are essential for maximizing agronomic potential, yet high P inputs and subsequent P losses can cause eutrophication of water bodies. There is a need to evaluate P contents in agricultural soils globally both from an agronomic and environmental perspective. This systematic review and meta-analysis estimated the pooled mean levels of P contents of Iran. In this study, data on available and total P contents of Iran's calcareous soils was compiled (main focus on Olsen P) and compared to (i) estimated Iranian background and global agricultural soil P contents, and (ii) agronomic and (iii) environmentally critical Olsen P values. The pooled mean estimate from the meta-analysis indicates that the levels of Olsen P across 425 soil samples (27 studies) were 21.3 mg kg-1 and total P across 190 soil samples (12 studies) 805.5 mg kg-1. Using 26 mg kg-1 as the agronomic critical Olsen P value above which no increase in crop yield occurs, crops grown on 61% of the soil samples in the investigated region would respond to P fertilizer and 20% of soils are currently in the optimum category (26-45 mg kg-1 Olsen P). The environmentally critical Olsen P value (~ 63 mg kg-1), defined as the amount above which P leaches from soil rapidly, was exceeded by 11% of soils with a further 4% of soils with elevated eutrophication risk. To maximize crop yields while maintaining a minimal risk of P leaching in Iran's calcareous soils, we suggest an ideal Olsen P of 26 mg kg-1. The outcomes from this study inform about the P status of Iranian soils and could help update recommendations for P fertilizer applications in calcareous soils globally. The framework presented here could further be adopted to evaluate the P status in other soil types.

An autoactive NB-LRR gene causes Rht13 dwarfism in wheat.

Semidwarfing genes have greatly increased wheat yields globally, yet the widely used gibberellin (GA)-insensitive genes Rht-B1b and Rht-D1b have disadvantages for seedling emergence. Use of the GA-sensitive semidwarfing gene Rht13 avoids this pleiotropic effect. Here, we show that Rht13 encodes a nucleotide-binding site/leucine-rich repeat (NB-LRR) gene. A point mutation in the semidwarf Rht-B13b allele autoactivates the NB-LRR gene and causes a height reduction comparable with Rht-B1b and Rht-D1b in diverse genetic backgrounds. The autoactive Rht-B13b allele leads to transcriptional up-regulation of pathogenesis-related genes including class III peroxidases associated with cell wall remodeling. Rht13 represents a new class of reduced height (Rht) gene, unlike other Rht genes, which encode components of the GA signaling or metabolic pathways. This discovery opens avenues to use autoactive NB-LRR genes as semidwarfing genes in a range of crop species, and to apply Rht13 in wheat breeding programs using a perfect genetic marker.

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.

Highly efficient phosphorus recovery from sludge and manure biochars using potassium acetate pre-treatment.

Pyrolysis converts nutrient-rich residues (e.g., sewage sludge and manures) into biochar with low levels of organic contaminants and high nutrient contents. However, the availability of phosphorus (P) as one of the key nutrients in such biochar tends to be low and new approaches are needed to enhance P-availability. In this work we tested and optimised one such method, doping biomass prior to pyrolysis with potassium (K) as potassium acetate. The treatment worked effectively in both pyrolysis units tested (microscale and lab-scale, continuous unit) and all three feedstocks (two types of sewage sludges and swine manure). The most dramatic effect was observed in the microscale pyrolysis unit at 400 °C where 5% K doping increased the water-extractable P content 700-fold to 43% of total P. Of the added K, on average 90% was retained in biochar after pyrolysis of which ∼50% was water-extractable. The proposed method enables conversion of low-value residues into valuable resources with agronomically relevant total and available P and K levels. This approach does not require specialised equipment or process modifications and is therefore easy to implement and relatively cheap (∼US$ 60-80 t-1 treated feedstock). It can present an urgently required solution to fulfil regulatory requirements for P-recovery.

Overgrowth mutants determine the causal role of gibberellin GA2oxidaseA13 in Rht12 dwarfism of wheat.

The induced dwarf mutant Rht12 was previously shown to have agronomic potential to replace the conventional DELLA mutants Rht-B1b/Rht-D1b in wheat. The Rht12 dwarfing gene is not associated with reduced coleoptile length (unlike the DELLA mutants) and it is dominant, characteristics which are shared with the previously characterized dwarfing genes Rht18 and Rht14. Using the Rht18/Rht14 model, a gibberellin (GA) 2-oxidase gene was identified in the Rht12 region on chromosome 5A. A screen for suppressor mutants in the Rht12 background identified tall overgrowth individuals that were shown to contain loss-of-function mutations in GA2oxidaseA13, demonstrating the role of this gene in the Rht12 dwarf phenotype. It was concluded that Rht12, Rht18, and Rht14 share the same height-reducing mechanism through the increased expression of GA 2-oxidase genes. Some of the overgrowth mutants generated in this study were semi-dwarf and taller than the original Rht12 dwarf, providing breeders with new sources of agronomically useful dwarfism.

A meta-analysis on biochar's effects on soil water properties - New insights and future research challenges.

Biochar can significantly alter water relations in soil and therefore, can play an important part in increasing the resilience of agricultural systems to drought conditions. To enable matching of biochar to soil constraints and application needs, a thorough understanding of the impact of biochar properties on relevant soil parameters is necessary. This meta-analysis of the available literature for the first time quantitatively assess the effect of not just biochar application, but different biochar properties on the full sets of key soil hydraulic parameters, i.e., the available water content (AWC), saturated hydraulic conductivity (Ksat), field capacity (FC), permanent wilting point (PWP) and total porosity (TP). The review shows that biochar increased soil water retention and decreased Ksat in sandy soils and increased Ksat and hence decreased runoff in clayey soils. On average, regardless of soil type, biochar application increased AWC (28.5%), FC (20.4%), PWP (16.7%) and TP (9.1%), while it reduced Ksat (38.7%) and BD (0.8%). Biochar was most effective in improving soil water properties in coarse-textured soils with application rates between 30 and 70 t/ha. The key factors influencing biochar performance were particle size, specific surface area and porosity indicating that both soil-biochar inter-particle and biochar intra-particle pores are important factors. To achieve optimum water relations in sandy soils (>60% sand and <20% clay), biochar with a small particle size (<2 mm) and high specific surface area and porosity should be applied. In clayey soil (>50% clay), <30 t/ha of a high surface area biochar is ideal.

Synergistic immobilization of potentially toxic elements (PTEs) by biochar and nanoparticles in alkaline soil.

Biochar and nanoparticle (NP) have the ability to sorb potentially toxic elements (PTEs) from soil and reduce toxicity and leaching into water bodies. However, there is need to tailor biochar formulations to soil types. In this study, we investigate the mobility and chemical forms of Cd, Cr, Cu, Ni, and Zn in a spiked, alkaline soil after amendment with combination of NPs (nano-Fe (NF), nano-clay (NC)) and biochars (almond shell 500 °C, walnut shell 400 °C) in different doses (0, 2.5, 5, and 10%). Many previous studies concluded biochar immobilized PTEs due to an increase in soil pH, which can be disregarded here (soil pH 7.9). In a twenty-week column leaching experiment biochar addition significantly decreased PTE leaching and NP addition further immobilized PTEs in most cases. On average almond biochar more effectively reduced Zn leaching and walnut biochar was more effective in decreasing the leaching of Cd, Cr, and Ni (e.g. 5% biochar reduced Cr leaching by 68%). Copper was immobilized effectively by both biochars. Nano-clay combined with walnut biochar performed best in all treatments, in particular for Cd, Ni, and Zn (e.g. 10% walnut biochar only and in combination with NC reduced Zn leaching by 14.2% and 58.5%, respectively). After amendment, PTEs were present in the Fe-Mn oxides, organic and residual fractions and less in the exchangeable fraction, reducing PTE availability and leachability. The results demonstrate that even for cationic PTEs that behave similarly in the environment optimal biochar-mineral formulations can differ.

Potassium doping increases biochar carbon sequestration potential by 45%, facilitating decoupling of carbon sequestration from soil improvement.

Negative emissions technologies offer an important tool to limit the global warming to <2 °C. Biochar is one of only a few such technologies, and the one at highest technology readiness level. Here we show that potassium as a low-concentration additive in biochar production can increase biochar's carbon sequestration potential; by up to 45% in this study. This translates to an increase in the estimated global biochar carbon sequestration potential to over 2.6 Gt CO2-C(eq) yr-1, thus boosting the efficiency of utilisation of limited biomass and land resources, and considerably improving the economics of biochar production and atmospheric carbon sequestration. In addition, potassium doping also increases plant nutrient content of resulting biochar, making it better suited for agricultural applications. Yet, more importantly, due to its much higher carbon sequestration potential, AM-enriched biochar facilitates viable biochar deployment for carbon sequestration purposes with reduced need to rely on biochar's abilities to improve soil properties and crop yields, hence opening new potential areas and scenarios for biochar applications.

Biochar Phosphorus Release Is Limited by High pH and Excess Calcium.

Aside from its use for improving soil properties, biochar is increasingly promoted as a direct nutrient provider for sustainable recycling of waste materials. However, incomplete understanding of the interacting factors that determine P release from biochar may limit the efficiency of P recycling from biochar to soil. In particular, the contrasting pH of biochar and soil need to be considered. In this study, soil-free biochar (rice [ L.] husk, 700°C) extractions were performed under different pH (4.6-9.9) and extractant conditions to test how solution composition affects biochar P release. When solution pH was in the range of 7.6 to 8.6 and excess Ca was present in the solution or in biochar, P release was low-only 1 to 7% of the total P was released compared with ∼20% under most other conditions. Importantly, we demonstrate that biochar total Ca concentration is closely related to P availability ( = 0.76) and could be used to predict biochar P release. The results suggest that for maximum P release, low Ca concentrations in biochar and (soil) solution are needed and/or a pH <7.5 at the soil-biochar interface. This novel understanding will help engineer sustainable biochar fertilizers optimized for P provision.

Toxicity screening of biochar-mineral composites using germination tests.

This study assessed the properties and toxicity (water cress germination trials) of 38 waste-derived, novel biochar-mineral composites (BMCs) produced via slow pyrolysis and hydrothermal carbonization (hydrochars). The biochars were produced from sewage sludge and compost-like output (CLO) by varying the type of mineral additive (zeolite, wood ash and lignite fly ash), the mineral-to-feedstock ratio and the carbonization process. While pure hydrochars completely inhibited germination of water cress, this effect was ameliorated by mineral additives. Seedlings grew best in pyrolysis chars and while wood ash addition decreased plant growth in many cases, 1:10 addition to CLO doubled germination rate. The factors responsible for the phytotoxicity can be attributed to pH, salinity and organic contaminants. Importantly, while pure minerals inhibited germination, conversion of minerals into BMCs reduced their inhibitory effects due to buffered release of minerals. Overall, mineral wastes (e.g., combustion ashes) and waste biomass can be used safely as sources of nutrients and stable organic carbon (for soil carbon sequestration) when converted into specific biochar-mineral composites, exploiting synergies between the constituents to deliver superior performance.

Correction to: Influence of pyrolysis temperature and production unit on formation of selected PAHs, oxy-PAHs, N-PACs, PCDDs, and PCDFs in biochar-a screening study.

The correct presentation of Figs. 1, 3 and Table 3 are shown in this paper.

Influence of pyrolysis temperature and production unit on formation of selected PAHs, oxy-PAHs, N-PACs, PCDDs, and PCDFs in biochar-a screening study.

The influence of reactor type and operating conditions of the pyrolysis unit on the final concentration of toxic contaminants in biochar remains unclear. Therefore, we determined the concentrations of polycyclic aromatic hydrocarbons (PAHs), oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs), nitrogen-containing polycyclic aromatic compounds (N-PACs), polychlorinated dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs) in biochars produced from three different feedstocks (softwood, wheat straw, and anaerobic digestate). Different scaled pyrolysis units (one batch and two continuous units) at two different temperatures (550 and 700 °C) were considered. The results revealed that the type of biomass had a significant influence on the PAH, oxy-PAH, and N-PAC content of the biochars. The configuration and type of the pyrolysis unit influenced only the wheat straw pyrolyzed at 550 °C. PCDDs and PCDFs occurred at very low levels in the biochars. In terms of PAH, PCDD, and PCDF content, the biochars assessed in this study represent a low risk to the environment, regardless of the temperature and type and size of the pyrolysis unit.

Bioavailability of phosphorus, other nutrients and potentially toxic elements from marginal biomass-derived biochar assessed in barley (Hordeum vulgare) growth experiments.

Biochars produced from marginal biomass feedstocks are a potential source of recycled nutrients for agriculture, but may also contain potentially toxic elements (PTEs) which can cause phytotoxicity. We assessed the potential for nutrient recycling from such materials against potential environmental risks in 17 biochars containing high concentrations of various PTEs and nutrients. Methods for investigating the risk of biochar-derived PTEs were developed and assessed. Short-term (21days) growth experiments with barley (Hordeum vulgare) in 5% biochar/sand mixtures were used to present the 'worst-case scenario' of high dose and low pH buffering. We compared plant nutrient and PTE concentrations with amounts extracted from the same biochars using 1M NH4NO3 or 0.01M CaCl2 (buffered and unbuffered, respectively) and Mehlich 3 to analyse whether such extractions could be used to predict bioavailability. The yields of barley grown with biochars "EPOCAD550", and "WLB550" were significantly higher than the control (p<0.05). Total phosphorus (P) concentration in above-ground biomass was higher than the control for the EPOCAD550 treatment (p<0.01). Both buffered and unbuffered 0.01M CaCl2 biochar extractions were significantly positively correlated with plant leaf concentration for six of the 18 elements investigated, more than any of the other extractions. CaCl2 extractions provided the most representative assessment of element bioavailability from marginal biochars compared to more resource-intensive growth experiments. Our results provide new insights into the bioavailability of elements in biochar and the standardisation of methods which accurately assess this attribute, which is necessary for promoting use of biochars from marginal biomass for recycling nutrients from wastewater and to agricultural production.

Risks and benefits of marginal biomass-derived biochars for plant growth.

In this study, 19 biochars from marginal biomass, representing all major biomass groups (woody materials, grass, an aquatic plant, anthropogenic wastes) were investigated regarding their content of available potentially toxic elements (PTEs) and nutrients (determined by NH4NO3-extractions) and their effects on cress (Lepidium sativum) seedling growth. The objective was to assess the potential and actual effects of biochar with increased PTE content on plant growth in the context of use in soil amendments and growing media. It showed that the percentage of available PTEs was highest for biochars produced at the highest treatment temperature (HTT) of 750°C. On average, however, for all 19 biochars, the percentage availability of Cu, Cr, Ni and Zn (<1.5% for all) was similar to the percentage availability reported in the literature for the same elements in soils at similar pH values which is a highly important finding. Most biochars exceeded German soil threshold values for NH4NO3-extractable PTEs, such as Zn (by up to 25-fold), As and Cd. Despite this, cress seedling growth tests with 5% biochar in sand did not show any correlations between inhibitory effects (observed in 5 of the 19 biochars) and the available PTE concentrations. Instead, the available K concentration and biochar pH were highly significantly, negatively correlated with seedling growth (K: p<0.001, pH: p=0.004). K had the highest available concentration of all elements and the highest percentage availability (47.7±19.7% of the total K was available). Consequently, available K contributed most to the osmotic pressure and high pH which negatively affected the seedlings. Although a potential risk if some of these marginal biomass-derived biochar were applied at high concentrations, e.g. 5% (>100tha(-1)), when applied at agriculturally realistic application rates (1-10tha(-1)), the resulting smaller increases in pH and available K concentration may actually be beneficial for plant growth.

High-VOC biochar-effectiveness of post-treatment measures and potential health risks related to handling and storage.

Biochar can contain volatile organic compounds (VOCs), formed and introduced during the pyrolysis process. In some pyrolysis units or under specific conditions during production, pyrolysis vapours can deposit on biochar in significant amounts resulting in high-VOC biochar. In this study, it was tested to which extent VOCs are released from such high-VOC biochars when openly stored, which post-treatment measures are most effective in reducing phytotoxic potential and whether the VOC emissions could exceed human health-related threshold values. It was shown that the initial VOC release of high-VOC biochars can exceed occupational exposure limit values and even after 2 months, the biochars still emitted VOCs exceeding air quality guideline values. Consequently, these specific high-VOC biochars pose health risks when handled or stored openly. Simple open-air storage turned out to be insufficient for VOC removal. Low temperature treatment, on the other hand, removed VOCs from the high-VOC biochars effectively and alleviated any human health risks and phytotoxic effects. In addition to the high-VOC biochars, a low-VOC biochar was tested which did not emit any VOCs and was even able to sorb VOCs from the VOC-rich biochar to a certain extent. Thermal treatment and blending with low-VOC biochar are methods which could be used in practise to treat high-VOC biochar, reducing VOC emissions. This study revealed significant new findings on the topic of VOCs in biochar which highlights the need to include VOCs in the list of priority contaminants in biochar.

Suitability of marginal biomass-derived biochars for soil amendment.

The term "marginal biomass" is used here to describe materials of little or no economic value, e.g. plants grown on contaminated land, food waste or demolition wood. In this study 10 marginal biomass-derived feedstocks were converted into 19 biochars at different highest treatment temperatures (HTT) using a continuous screw-pyrolysis unit. The aim was to investigate suitability of the resulting biochars for land application, judged on the basis of potentially toxic element (PTE) concentration, nutrient content and basic biochar properties (pH, EC, ash, fixed carbon). It was shown that under typical biochar production conditions the percentage content of several PTEs (As, Al, Zn) and nutrients (Ca, Mg) were reduced to some extent, but also that biochar can be contaminated by Cr and Ni during the pyrolysis process due to erosion of stainless steel reactor parts (average+82.8% Cr, +226.0% Ni). This can occur to such an extent that the resulting biochar is rendered unsuitable for soil application (maximum addition +22.5 mg Cr kg(-1) biochar and +44.4 mg Ni kg(-1) biochar). Biomass grown on land heavily contaminated with PTEs yielded biochars with PTE concentrations above recommended threshold values for soil amendments. Cd and Zn were of particular concern, exceeding the lowest threshold values by 31-fold and 7-fold respectively, despite some losses into the gas phase. However, thermal conversion of plants from less severely contaminated soils, demolition wood and food waste anaerobic digestate (AD) into biochar proved to be promising for land application. In particular, food waste AD biochar contained very high nutrient concentrations, making it interesting for use as fertiliser.

Inherent organic compounds in biochar--Their content, composition and potential toxic effects.

Pyrolysis liquids consist of thermal degradation products of biomass in various stages of its decomposition. Therefore, if biochar gets affected by re-condensed pyrolysis liquids it is likely to contain a huge variety of organic compounds. In this study the chemical composition of such compounds associated with two contaminated, high-volatile organic compound (VOC) biochars were investigated and compared with those for a low-VOC biochar. The water-soluble organic compounds with the highest concentrations in the two high-VOC biochars were acetic, formic, butyric and propionic acids; methanol, phenol, o-, m- and p-cresol, and 2,4-dimethylphenol, all with concentrations over 100 µg g(-1). The concentrations of 16 US EPA PAHs determined by 36 h toluene extractions were 6.09 µg g(-1) for the low-VOC biochar. For high-VOC biochar the total concentrations were 53.42 µg g(-1) and 27.89 µg g(-1), while concentrations of water-soluble PAHs ranged from 1.5 to 2 µg g(-1). Despite the concentrations of PAHs exceeding biochar guideline values, it was concluded that, for these particular biochars, the biggest concern for application to soil would be the co-occurrence of VOCs such as low molecular weight (LMW) organic acids and phenols, as these can be highly mobile and have a high potential to cause phytotoxic effects. Therefore, based on results of this study we strongly suggest for VOCs to be included among criteria for assessment of biochar quality.

Mobile organic compounds in biochar - a potential source of contamination - phytotoxic effects on cress seed (Lepidium sativum) germination.

Biochar can be contaminated during pyrolysis by re-condensation of pyrolysis vapours. In this study two biochar samples contaminated by pyrolysis liquids and gases to a high degree, resulting in high volatile organic compound (high-VOC) content, were investigated and compared to a biochar with low volatile organic compound (low-VOC) content. All biochar samples were produced from the same feedstock (softwood pellets) under the same conditions (550 °C, 20 min mean residence time). In experiments where only gaseous compounds could access germinating cress seeds (Lepidium sativum), application amounts ranging from 1 to 30 g of high-VOC biochar led to total inhibition of cress seed germination, while exposure to less than 1 g resulted in only partial reduction. Furthermore, leachates from biochar/sand mixtures (1, 2, 5 wt.% of biochar) induced heavy toxicity to germination and showed that percolating water could dissolve toxic compounds easily. Low-VOC biochar didn't exhibit any toxic effects in either germination test. Toxicity mitigation via blending of a high-VOC biochar with a low-VOC biochar increased germination rate significantly. These results indicate re-condensation of VOCs during pyrolysis can result in biochar containing highly mobile, phytotoxic compounds. However, it remains unclear, which specific compounds are responsible for this toxicity and how significant re-condensation in different pyrolysis units might be.