Experiments on Vapor Pressure of KCl at Different Molar Fractions in Mixtures of KCl + K2SO4.

The objective of this paper is to measure the vapor pressure of potassium chloride (KCl) in its mixture with potassium sulfate (K2SO4). Evaporation behavior of pure salts of KCl, K2SO4, and their mixtures at different molar fractions were examined using a simultaneous thermogravimetric analyzer (STA) at different temperatures with a pair of crucibles (outer: platinum; inner: alumina). The dependence of the vapor pressure of KCl on its molar fraction in mixtures of KCl + K2SO4 was obtained on the basis of relative pressure. Results show that vapor pressure of KCl is increased to 1.2 times when a small amount of K2SO4 (molar fraction from 0.05 to 0.20) is added. Evaporation of KCl will be inhibited by K2SO4 when the molar fraction of K2SO4 is higher than 0.27, which is its fraction in the eutectic system of KCl + K2SO4. Vapor pressure of KCl decreases significantly with increasing molar fractions of K2SO4 at its inhibition scope.

A re-analysis of NH4+ sorption on biochar: Have expectations been too high?

Sorption of nutrients such as NH4+ is often quoted as a critical property of biochar, explaining its value as a soil amendment and a filter material. However, published values for NH4+ sorption to biochar vary by more than 3 orders of magnitude, without consensus as to the source of this variability. This lack of understanding greatly limits our ability to use quantitative sorption measurements towards product design. Here, our objective was to conduct a quantitative analysis of the sources of variability, and infer which biochar traits are more favourable to high sorption capacity. To do so, we conducted a standardized remodelling exercise of published batch sorption studies using Langmuir sorption isotherm. We excluded studies presenting datasets that either could not be reconciled with the standard Langmuir sorption isotherm or generated clear outliers. Our analysis indicates that the magnitude of sorption capacity of unmodified biochar for NH4+ is lower than previously reported, with a median of 4.2 mg NH4+ g-1 and a maximum reported sorption capacity of 22.8 mg NH4+ g-1. Activation resulted in a significant relative improvement in sorption capacity, but absolute improvements remain modest, with a maximum reported sorption of 27.56 mg NH4+ g-1 for an activated biochar. Methodology appeared to substantially impact sorption estimates, especially practices such as pH control of batch sorption solution and ash removal. Our results highlight some significant challenges in the quantification of NH4+ sorption by biochar and our curated data set provides a potentially valuable scale against which future estimates can be assessed.

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.

Organic coating on biochar explains its nutrient retention and stimulation of soil fertility.

Amending soil with biochar (pyrolized biomass) is suggested as a globally applicable approach to address climate change and soil degradation by carbon sequestration, reducing soil-borne greenhouse-gas emissions and increasing soil nutrient retention. Biochar was shown to promote plant growth, especially when combined with nutrient-rich organic matter, e.g., co-composted biochar. Plant growth promotion was explained by slow release of nutrients, although a mechanistic understanding of nutrient storage in biochar is missing. Here we identify a complex, nutrient-rich organic coating on co-composted biochar that covers the outer and inner (pore) surfaces of biochar particles using high-resolution spectro(micro)scopy and mass spectrometry. Fast field cycling nuclear magnetic resonance, electrochemical analysis and gas adsorption demonstrated that this coating adds hydrophilicity, redox-active moieties, and additional mesoporosity, which strengthens biochar-water interactions and thus enhances nutrient retention. This implies that the functioning of biochar in soil is determined by the formation of an organic coating, rather than biochar surface oxidation, as previously suggested.

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

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

Surface properties and chemical composition of corncob and miscanthus biochars: effects of production temperature and method.

Biochar properties vary, and characterization of biochars is necessary for assessing their potential to sequester carbon and improve soil functions. This study aimed at assessing key surface properties of agronomic relevance for products from slow pyrolysis at 250-800 °C, hydrothermal carbonization (HTC), and flash carbonization. The study further aimed at relating surface properties to current characterization indicators. The results suggest that biochar chemical composition can be inferred from volatile matter (VM) and is consistent for corncob and miscanthus feedstocks and for the three tested production methods. High surface area was reached within a narrow temperature range around 600 °C, whereas cation exchange capacity (CEC) peaked at lower temperatures. CEC and pH values of HTC chars differed from those of slow pyrolysis biochars. Neither CEC nor surface area correlated well with VM or atomic ratios. These results suggest that VM and atomic ratios H/C and O/C are good indicators of the degree of carbonization but poor predictors of the agronomic properties of biochar.