Long-term TNT and DNT contamination: 1-D modeling of natural attenuation in the vadose zone: case study, Portugal

The vadose zone of a trinitrotoluene (TNT) and dinitrotoluene (DNT) contaminated site was investigated to assess the mobility of those explosives under natural conditions. Located in the left margin of the River Tejo Basin, Portugal, the site is located on unconsolidated sediments. Wastewaters associated with the 50-year explosives production were disposed in excavated ponds, from where water would infiltrate and pollute the unsaturated and saturated parts of the local aquifers. Two boreholes were drilled to 9 m depth in such a former waste pond to investigate the contaminant's fate in the vadose zone. Sediment samples were taken every 1-2 m for analysis of the polynitroaromatics (p-NACs) and organic volatile compounds, pH, organic carbon content, cation exchange capacity and grain size analysis. The main contaminant was TNT representing >70 % of the total p-NACs concentration that peaked approximately 7 mg/kg in one borehole, even if the median in both boreholes was of similar to 1 mg/kg. DNT was 4-30 % of the total p-NACs and nitrotoluene (NT), up to 5 %. No other (volatile) organic compound was detected. The predominance of TNT as the main contaminant implies that any natural mass reduction has been inefficient to clean the site. Several 1-D model simulations of p-NACs cleaning of the vadose zone under natural conditions indicated that the most probable scenario of combined advection and partitioning will only remove TNT after 10's of years, whereas DNT and NT will hardly be removed. Such low concentrations and long times for the p-NACs removal, suggest that by now those compounds have been washed-out to a level below standard limits

Glossary of terms used in biochar research (IUPAC Technical Report).

Biochar is the solid carbonaceous product of biomass pyrolysis. The properties of biochar depend on the biomass feedstock as well as the pyrolysis temperature and time. Therefore, biochars with different properties and functionalities can be produced. Biochar research has been intensive in the past 15 years, focusing mainly on soil applications, wastewater treatment, and contaminant remediation. However, a formal definition of biochar and related terms is missing, which hinders the standardization of scientific results worldwide and the scaling-up of research at the industrial level. Furthermore, an official terminology may promote the development of a harmonized legal framework for biochar production and applications, both at regional and national levels. This glossary of terms consists of 178 scientifically sound definitions of the most commonly used terms in biochar research. The definitions of this glossary are interconnected, allowing the reader to further explore the synergies between terms. The distribution of terms reflects the multidisciplinarity of biochar research: chemistry, material science and engineering, and soil science are the main disciplines represented here. The list of terms is by no means exhaustive and the strategic objective of this effort is to develop a dynamic document in which more terms will be added in the future, and the existing ones will be refined, as biochar research evolves.On-line first

Hydrochars as Emerging Biofuels: Recent Advances and Application of Artificial Neural Networks for the Prediction of Heating Values

In this study, the growing scientific field of alternative biofuels was examined, with respect to hydrochars produced from renewable biomasses. Hydrochars are the solid products of hydrothermal carbonization (HTC) and their properties depend on the initial biomass and the temperature and duration of treatment. The basic (Scopus) and advanced (Citespace) analysis of literature showed that this is a dynamic research area, with several sub-fields of intense activity. The focus of researchers on sewage sludge and food waste as hydrochar precursors was highlighted and reviewed. It was established that hydrochars have improved behavior as fuels compared to these feedstocks. Food waste can be particularly useful in co-hydrothermal carbonization with ash-rich materials. In the case of sewage sludge, simultaneous P recovery from the HTC wastewater may add more value to the process. For both feedstocks, results from large-scale HTC are practically non-existent. Following the review, related data from the years 2014–2020 were retrieved and fitted into four different artificial neural networks (ANNs). Based on the elemental content, HTC temperature and time (as inputs), the higher heating values (HHVs) and yields (as outputs) could be successfully predicted, regardless of original biomass used for hydrochar production. ANN3 (based on C, O, H content, and HTC temperature) showed the optimum HHV predicting performance (R2 0.917, root mean square error 1.124), however, hydrochars’ HHVs could also be satisfactorily predicted by the C content alone (ANN1, R2 0.897, root mean square error 1.289)

A complementary analysis of the porous structure of biochars obtained from biomass

Abstract This paper presents the results of the analysis of the porous structure of biochars produced from biomass, namely eucalyptus, wood chips, pruning waste and rice husk. The structural analysis was carried out using the BET, the t-plot, the NLDFT and the LBET methods, which yielded not only complementary information on the adsorptive properties of obtained biochars from these materials, but also information on the usefulness of the structural analysis methods in question for the research into an effect of the technology of carbonaceous adsorbent preparation.</jats:p

Assessment of Orange Peel Hydrochar as a Soil Amendment: Impact on Clay Soil Physical Properties and Potential Phytotoxicity

Purpose: The main objectives of this work were the following: (1) to investigate the applicability of orange peel hydrochar as a soil amendment for improving the physical properties of a compacted, clay soil and (2) to study the growth of maize on substrates composed of clay soil and hydrochar and determine any potential phytotoxic effects. Methods: The effect on soil’s bulk density (BD), aeration, water holding capacity (WHC), and hydraulic conductivity were examined with hydrochar additions of 5, 10 and 15% (w/w) and determined by conventional laboratory methods. Potential phytotoxic effects were determined through the Zucconi germination index on fresh, diluted and 4-week old undiluted hydrochar extracts. The effect of hydrochar on maize growth was studied in clay soil (as reference), clay soil with 5% (w/w) fresh hydrochar, clay soil with 5% (w/w) of 4-week-old hydrochar and clay soil with 5% (w/w) biochar (for comparison). Results: At an application rate of 5% (w/w) hydrochar, the bulk density was reduced from 1.35 to 1.22 g/cm3, the air-filled porosity was increased from 33 to 37% and the saturated hydraulic conductivity from 0.96 to 1.01 cm/h. The water holding capacity remained practically unchanged, however it was considerably reduced at higher application rates. The seed germination test indicated strong phytotoxicity of the fresh, undiluted hydrochar extract, which was reduced when the extract was diluted or the hydrochar allowed to mature for 4 weeks. The pot tests indicated that hydrochar did not improve the yield of maize, probably due to the presence of phytotoxic substances. Conclusions: This study demonstrated a new valorization pathway for a significant agricultural waste. Additionally, it proved the applicability of orange peel hydrochar for improving the physical properties of clay soil. However, due to phytotoxic effects, further work is required before a field application is considered. © 2018 Springer Nature B.V

Removal of 241Am from Aqueous Solutions by Adsorption on Sponge Gourd Biochar

Luffa cylindrica biomass was converted to biochar and the removal of 241Am by pristine and oxidized biochar fibers was investigated in laboratory and environmental water samples. This species has the added advantage of a unique microsponge structure that is beneficial for the production of porous adsorbents. The main purpose of this study was to valorize this biomass to produce an efficient adsorbent and investigate its performance in radionuclide-contaminated waters. Following the preparation of Am3+ solutions at a concentration of 10&minus;12 mol/L, the adsorption efficiency (Kd) was determined as a function of pH, adsorbent mass, ionic strength, temperature, and type of aqueous solution by batch experiments. At the optimum adsorbent dose of 0.1 g and pH value of 4, a log10Kd value of 4.2 was achieved by the oxidized biochar sample. The effect of temperature and ionic strength indicated that adsorption is an endothermic and entropy-driven process (&Delta;H&deg; = &minus;512 kJ mol&minus;1 and &Delta;S&deg; = &minus;1.2 J K&minus;1 mol&minus;1) leading to the formation of inner-sphere complexes. The adsorption kinetics were relatively slow (24 h equilibrium time) due to the slow diffusion of the radionuclide to the biochar surface and fitted well to the pseudo-first-order kinetic model. Oxidized biochar performed better compared to the unmodified sample and overall appears to be an efficient adsorbent for the treatment of 241Am-contaminated waters, even at ultra-trace concentrations