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.
Soil amendment with pyrogenic carbon (biochar) is discussed as strategy to improve soil fertility to enable economic plus environmental benefits. In temperate soils, however, the use of pure biochar ...mostly has moderately-negative to -positive yield effects. Here we demonstrate that co-composting considerably promoted biochars' positive effects, largely by nitrate (nutrient) capture and delivery. In a full-factorial growth study with Chenopodium quinoa, biomass yield increased up to 305% in a sandy-poor soil amended with 2% (w/w) co-composted biochar (BC(comp)). Conversely, addition of 2% (w/w) untreated biochar (BC(pure)) decreased the biomass to 60% of the control. Growth-promoting (BC(comp)) as well as growth-reducing (BC(pure)) effects were more pronounced at lower nutrient-supply levels. Electro-ultra filtration and sequential biochar-particle washing revealed that co-composted biochar was nutrient-enriched, particularly with the anions nitrate and phosphate. The captured nitrate in BC(comp) was (1) only partly detectable with standard methods, (2) largely protected against leaching, (3) partly plant-available, and (4) did not stimulate N2O emissions. We hypothesize that surface ageing plus non-conventional ion-water bonding in micro- and nano-pores promoted nitrate capture in biochar particles. Amending (N-rich) bio-waste with biochar may enhance its agronomic value and reduce nutrient losses from bio-wastes and agricultural soils.
In this paper, a new quantitative approach for estimating the structural and functional connectivity inside soil by Fast Field Cycling (FFC) NMR relaxometry is presented, tested by measurements ...carried out in three samples with different texture characteristics. Measurements by FFC NMR relaxometry have been carried out using water-suspended samples and Proton Larmor frequencies (νL) ranging in the 0.015–35 MHz interval. Two non-degraded soil samples, with different textural characteristics, and a degraded soil collected in a badland area, were analyzed. For a given soil and any applied Proton Larmor frequency, the distribution of the longitudinal relaxation times, T1, (i.e., relaxogram) measured by FFC NMR has been integrated, and the resulting S-shaped curve (i.e., relaxogram integration curve) was represented, for the first time, by Gumbel’s diagram. This new representation of the relaxogram integration curve, transforming the S-shaped curve into a straight line, allowed for distinguishing three linear components, corresponding to three different relaxation time ranges, characterized by three different slopes. Two points, identified by the abrupt slope changes of the relaxogram integration curve plotted in Gumbel’s diagram, are used to identify two characteristic values of relaxation time, T1A and T1B, which define three well-known pore size classes (T1 < T1A micro-pores, T1A < T1 < T1B meso-pores, and T1 > T1B macro-pores). The relaxogram integration curve allowed for calculating the non-exceeding empirical cumulative frequency, F(T1), corresponding to the characteristic T1A and T1B values. The analysis demonstrated that the relaxogram can be used to determine the pore-size ranges of each investigated sample. Finally, using the slope values of the three components of the relaxogram integration curve, a new definition of the Structural Connectivity Index, SCI, and Functional Connectivity Index, FCI, was proposed.
The increasing use of nanoparticles is causing a threat to the environment and humans. The aim of this work was to evaluate the effects of the quenching procedure of biochar production on the biochar ...capacity to retain the CeO2 nanoparticle (CeO2NP) in soil. The effects on Lepidium sativum L. (watercress) were considered. Two biochars were produced from fir wood pellets under the same pyrolysis conditions but with different quenching procedures: dry quenching and wet quenching. The two biochars (BCdryQ and BCwetQ) were separately added to a CeO2NP-spiked soil (1000 mg kg−1) at the dose 5%DW and placed in 12 lysimeters under controlled conditions. Lepidium sativum L. seeds were sowed on each lysimeter. The lysimeters were irrigated once a week for 7 weeks, and the leachates were collected. At the end of the experiment, the aboveground biomass was harvested; the total number of plants and the number of plants at the flowering stage were counted, and the height of the tallest plant and the total dry biomass were measured. The data showed that the quenching procedure influences the CeO2NP retention in soil, and BCdryQ can reduce the leaching of the nanoparticles. Biochar significantly increased the flowering in plants, and BCwetQ reduced the biomass production. This work highlights the importance of the biochar production process for soil applications. The production settings are crucial in determining the efficacy of the product for its ultimate use.
Some composite materials have been prepared, constituted by a cyclodextrin-
-urethane-based nanosponge matrix in which a reduced graphene oxide/silver nanoparticles photocatalyst has been dispersed. ...Different chain extenders were employed for designing the nanosponge supports, in such a way as to decorate their hyper-cross-linked structure with diverse functionalities. Moreover, two different strategies were explored to accomplish the silver loading. The obtained systems were successfully tested as catalysts for the photodegradation of emerging pollutants such as model dyes and drugs. Enhancement of the photoactive species performance (up to nine times), due to the synergistic local concentration effect exerted by the nanosponge, could be assessed. Overall, the best performances were shown by polyamine-decorated materials, which were able to promote the degradation of some particularly resistant drugs. Some methodological issues pertaining to data collection are also addressed.
Biochars from wood chips (WC) and corn cobs (CC) were prepared by slow pyrolysis and used for sorption separation of erythrosine B (EB) and thioflavin T (TT) in batch experiments. Biochar-based ...adsorbents were extensively characterized using FTIR, XRD, SEM-EDX, and XPS techniques. The kinetics studies revealed that adsorption on external surfaces was the rate-limiting step for the removal of TT on both WC and CC biochar, while intraparticle diffusion was the rate-limiting step for the adsorption of EB. Maximal experimental adsorption capacities
of TT reached 182 ± 5 (WC) and 45 ± 2 mg g
(CC), and EB 12.7 ± 0.9 (WC) and 1.5 ± 0.4 mg g
(CC), respectively, thereby indicating a higher affinity of biochars for TT. The adsorption mechanism was found to be associated with π-π interaction, hydrogen bonding, and pore filling. Application of the innovative dynamic approach based on fast-field-cycling NMR relaxometry indicates that variations in the retention of water-soluble dyes could be explained by distinct water dynamics in the porous structures of WC and CC. The obtained results suggest that studied biochars will be more effective in adsorbing of cationic than anionic dyes from contaminated effluents.
Nuclear magnetic resonance (NMR) techniques are largely employed in several fields. As an example, NMR spectroscopy is used to provide structural and conformational information on pure systems, while ...affording quantitative evaluation on the number of nuclei in a given chemical environment. When dealing with relaxation, NMR allows understanding of molecular dynamics, i.e., the time evolution of molecular motions. The analysis of relaxation times conducted on complex liquid–liquid and solid–liquid mixtures is directly related to the nature of the interactions among the components of the mixture. In the present review paper, the peculiarities of low resolution fast field-cycling (FFC) NMR relaxometry in soil science are reported. In particular, the general aspects of the typical FFC NMR relaxometry experiment are firstly provided. Afterwards, a discussion on the main mathematical models to be used to “read” and interpret experimental data on soils is given. Following this, an overview on the main results in soil science is supplied. Finally, new FFC NMR-based hypotheses on nutrient dynamics in soils are described
The remediation of the highly contaminated site around the former chemical plant of ACNA (near Savona) in Northern Italy is a top priority in Italy. The aim of the present work was to contribute in ...finding innovative and environmental-friendly technology to remediate soils from the ACNA contaminated site. Two soils sampled from the ACNA site (A and B), differing in texture and amount and type of organic contaminants, were subjected to soil washings by comparing the removal efficiency of water, two synthetic surfactants, sodium dodecylsulphate (SDS) and Triton X-100 (TX100), and a solution of a natural surfactant, a humic acid (HA) at its critical micelle concentration (CMC). The extraction of pollutants by sonication and soxhlet was conducted before and after the soil washings. Soil A was richer in polycyclic aromatic hydrocarbons, whereas soil B had a larger content of thiophenes. Sonication resulted more analytically efficient in the fine-textured soil B. The coarse-textured soil A was extracted with a general equal efficiency also by soxhlet. Clean-up by water was unable to exhaustively remove contaminants from the two soils, whereas all the organic surfactants revealed very similar efficiencies (up to 90%) in the removal of the contaminants from the soils. Hence, the use of solutions of natural HAs appears as a better choice for soil washings of highly polluted soils due to their additional capacity to promote microbial activity, in contrast to synthetic surfactants, for a further natural attenuation in washed soils.
Solutions of natural humic acids appear to be a better choice for washing highly polluted soils.
Resource recovery from wastewater is very important in view of a circular economy approach in the water field. Among the different technologies applied to realize circular economy, an attractive ...option is the use of nutrient-enriched media that can be utilized as slow-release fertilizers. Zeolites have been re-discovered for their key role in ammonium (NH4+) adsorption from treated wastewater. Although many studies have been carried out to assess the ability of zeolites to adsorb NH4+, only few papers concerning NH4+ desorption from zeolites are available in the literature. Therefore, this study investigated NH4+ desorption from mineralogically different zeolites, before (ZNS and ZNC) and after (ZSS and ZSC) their treatment with sodium chloride. The zeolites differed in mordenite content. The amount of the desorbed NH4+ varied from 78 to 84% of the total NH4+ adsorbed. In particular, the NaCl-treated materials showed the largest desorption (27.6 ± 0.2 mg L−1, and 27.9 ± 0.7 mg L−1, ZSS, and ZSC, respectively) as compared to the untreated zeolites (22.9 ± 0.3 mg L−1, and 24.2 ± 0.3 mg L−1, ZNS, and ZNC, respectively) because of the different affinity of the cations for the zeolite surface. A monomodal pseudo-first-order model best approximated the desorption kinetics, suggesting only one mechanism of NH4+ desorption from zeolites. Such a mechanism is based on the ion exchange between dissolved Na+ and adsorbed NH4+. The desorption kinetics also showed that NH4+ desorbed slower from the NaCl-treated zeolites than the untreated ones. This effect was explained by the different affinity of Na+ and NH4+ for the zeolite surfaces as due to the diverse sizes of the Na+ and NH4+ hydration spheres. By revealing the effect of zeolite mineralogy and surface treatments in the desorption of NH4+, this study can suggest new and effective synthetic strategies for the achievement of cheap new materials to be applied in environmental remediation within a circular economy perspective.
Biochar is a porous material obtained by biomass thermal degradation in oxygen-starved conditions. It is nowadays applied in many fields. For instance, it is used to synthesize new materials for ...environmental remediation, catalysis, animal feeding, adsorbent for smells, etc. In the last decades, biochar has been applied also to soils due to its beneficial effects on soil structure, pH, soil organic carbon content, and stability, and, therefore, soil fertility. In addition, this carbonaceous material shows high chemical stability. Once applied to soil it maintains its nature for centuries. Consequently, it can be considered a sink to store atmospheric carbon dioxide in soils, thereby mitigating the effects of global climatic changes. The literature contains plenty of papers dealing with biochar’s environmental effects. However, a discrepancy exists between studies dealing with biochar applications and those dealing with the physical-chemistry behind biochar behavior. On the one hand, the impression is that most of the papers where biochar is tested in soils are based on trial-and-error procedures. Sometimes these give positive results, sometimes not. Consequently, it appears that the scientific world is divided into two factions: either supporters or detractors. On the other hand, studies dealing with biochar’s physical-chemistry do not appear helpful in settling the factions’ problem. This review paper aims at collecting all the information on physical-chemistry of biochar and to use it to explain biochar’s role in different fields of application.
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