Synthesis of Porous BPPO-Based Anion Exchange Membranes for Acid Recovery Via Diffusion Dialysis

Diffusion dialysis (DD) is an anion exchange membrane-based functional separation process used for acid recovery. TMA (trimethylamine) and BPPO (brominated poly (2,6-dimethyl-1,4-phenylene oxide) were utilized in this manuscript to formulate AEMs (anion exchange membranes) for DD (diffusion dialysis) using the phase-inversion technique. FTIR (Fourier transfer infrared) analysis, proton NMR spectroscopy, morphology, IEC (ion exchange capacity), LER (linear expansion ratio), CR (fixed group concentration), WR (water uptake/adsorption), water contact angle, chemical, and thermal stability, were all used to evaluate the prepared membranes. The effect of TMA content within the membrane matrix on acid recovery was also briefly discussed. It was reported that porous AEMs have a WR of 149.6% to 233.8%, IEC (ion exchange capacity) of 0.71 to 1.43 mmol/g, CR (fixed group concentration) that ranged from 0.0046 mol/L to 0.0056 mol/L, LER of 3.88% to 9.23%, and a water contact angle of 33.10° to 78.58°. The UH (acid dialysis coefficients) for designed porous membranes were found to be 0.0043 to 0.012 m/h, with separation factors (S) ranging from 13.14 to 32.87 at the temperature of 25 °C. These observations are comparable to those found in the DF-120B commercial membrane with UH of 0.004 m/h and S of 24.3 m/h at the same temperature (25 °C). This porous membranes proposed in this paper are excellent choices for acid recovery through the diffusion dialysis process.

Low-Impact Development (LID) in Coastal Watersheds: Infiltration Swale Pollutant Transfer in Transitional Tropical/Subtropical Climates

The control of runoff pollution is one of the advantages of low-impact development (LID) or sustainable drainage systems (SUDs), such as infiltration swales. Coastal areas may have characteristics that make the implementation of drainage systems difficult, such as sandy soils, shallow aquifers and flat terrains. The presence of contaminants was investigated through sampling and analysis of runoff, soil, and groundwater from a coastal region served by an infiltration swale located in southern Brazil. The swale proved to be very efficient in controlling the site’s urban drainage volumes even under intense tropical rainfall. Contaminants of Cd, Cu, Pb, Zn, Cr, Fe, Mn and Ni were identified at concentrations above the Brazilian regulatory limit (BRL) in both runoff and groundwater. Soil concentrations were low and within the regulatory limits, except for Cd. The soil was predominantly sandy, with neutral pH and low ionic exchange capacity, characteristic of coastal regions and not very suitable for contaminant retention. Thus, this kind of structure requires improvements for its use in similar environments, such as the use of adsorbents in soil swale to increase its retention capacity.

Municipal sewage sludge as a source of microelements in sustainable plant production: a laboratory lysimeter study

The aim of the work was to characterize the samples of sewage sludge (SSL) originated from the Wastewater Treatment Plant Piešťany (TAVOS, a.s., Trnava, Slovakia) in terms of their potential application into the soils. Within the physico-chemical characterization of SSL, the samples were analysed in terms of the values of pH, cation exchange capacity (CEC), total organic carbon (TOC), water holding capacity (WHC), as well as the presence of heavy metals. It was found that SSL contained significant amounts of microelements Zn (1,269 mg.kg-1, d.w.) and Cu (224 mg.kg-1, d.w.). Laboratory lysimeter experiments involving the application of SSL into the top layer of agriculturally used soil (0 – 10 cm) forming a soil column, in which seedlings of tobacco (Nicotiana tabacum L.) were cultivated, showed that in the case of SSL application in the highest permitted amounts (15 t.ha-1) only 0.11 % Zn and 0.07 % Cu were released into the soil eluate during a 28 day of exposure, while in tobacco plants 0.13 % Zn and 0.05 % Cu were accumulated from the total amount of Zn and Cu originated from the application of SSL (Zn – 133 mg and Cu – 23.5 mg). When applying SSL in amount 30 t.ha-1 i.e., in the dose exceeding the permitted limits, only 0.02 % Zn and 0.04 % Cu were released into the soil eluate and 0.16 % Zn and 0.09 % Cu were accumulated in tobacco plants from the applied amount of SSL (Zn – 267 mg and Cu – 47.0 mg).

Aliphatic Anion Exchange Ionomers with Long Spacers and No Ether Links by Ziegler–Natta Polymerization: Properties and Alkaline Stability

In this work we report the synthesis of poly(vinylbenzylchloride-co-hexene) copolymer grafted with N,N-dimethylhexylammonium groups to study the effect of an aliphatic backbone without ether linkage on the ionomer properties. The copolymerization was achieved by the Ziegler–Natta method, employing the complex ZrCl4 (THF)2 as a catalyst. A certain degree of crosslinking with N,N,N′,N′-tetramethylethylenediamine (TEMED) was introduced with the aim of avoiding excessive swelling in water. The resulting anion exchange polymers were characterized by 1H-NMR, FTIR, TGA, and ion exchange capacity (IEC) measurements. The ionomers showed good alkaline stability; after 72 h of treatment in 2 M KOH at 80 °C the remaining IEC of 76% confirms that ionomers without ether bonds are less sensitive to a SN2 attack and suggests the possibility of their use as a binder in a fuel cell electrode formulation. The ionomers were also blended with polyvinyl alcohol (PVA) and crosslinked with glutaraldehyde. The water uptake of the blend membranes was around 110% at 25 °C. The ionic conductivity at 25 °C in the OH− form was 29.5 mS/cm.

Short-Term Abandonment versus Mowing in a Mediterranean-Temperate Meadow: Effects on Floristic Composition, Plant Functionality, and Soil Properties—A Case Study

Hay meadows are secondary grasslands maintained by mowing, and their ecological importance resides in the inherent biodiversity and carbon stocking. We investigated the plant community and soil properties of a sub humid acid grassland near the Fucecchio marshes (Italy), managed as a hay meadow, mowed once a year, and not fertilized. Part of the meadow had been abandoned for three years. We analysed the soil properties (i.e., organic carbon and total nitrogen content, available phosphorus, pH, cation-exchange capacity, texture, and conductibility) and the plant community structure (composition, functionality, and species richness) of the two sides of the meadow (mowed and abandoned). Our aim was to highlight the changes in soil properties and vegetation community, and to find out to what extent abandonment can affect those dynamics. Our results showed that after short-term abandonment, soil pH, C and N increased; litter biomass and perennial forbs increased; and annual forbs decreased. New species colonising after abandonment, thus enriching the flora, may keep spreading and eventually hinder the growth of the specialists if mowing is not resumed. Certain valuable meadow habitats need constant human intervention to maintain their peculiar vegetation, most especially if they are a buffer zone in the proximity of natural protected areas.

Physicochemical Characterization of Cherry Pits-Derived Biochar

Although the suitability of some biochars for contaminants’ sorption separation has been established, not all potential feedstocks have been explored and characterized. Here, we physicochemically characterized cherry pit biochar (CPB) pyrolyzed from cherry pit biomass (CP) at 500 °C, and we assessed their As and Hg sorption efficiencies in aqueous solutions in comparison to activated carbon (AC). The basic physicochemical and material characterization of the studied adsorbents was carried out using pH, electrical conductivity (EC), cation exchange capacity (CEC), concentration of surface functional groups (Boehm titration), and surface area (SA) analysis; elemental C, H, N analysis; and Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM–EDX). AsO43− anions and Hg2+ cations were selected as model contaminants used to test the sorption properties of the sorption materials. Characterization analyses confirmed a ninefold increase in SA in the case of CPB. The total C concentration increased by 26%, while decreases in the total H and N concentrations were observed. The values of carbonate and ash contents decreased by about half due to pyrolysis processes. The concentrations of surface functional groups of the analyzed biochar obtained by Boehm titration confirmed a decrease in carboxyl and lactone groups, while an increase in phenolic functional groups was observed. Changes in the morphology and surface functionality of the pyrolyzed material were confirmed by SEM–EDX and FTIR analyses. In sorption experiments, we found that the CPB showed better results in the sorption separation of Hg2+ than in the sorption separation of AsO43−. The sorption efficiency for the model cation increased in the order CP < CPB < AC and, for the model anion, it increased in the order CPB < CP < AC.

Ozonized biochar filtrate effects on the growth of Pseudomonas putida and cyanobacteria Synechococcus elongatus PCC 7942

Background Biochar ozonization was previously shown to dramatically increase its cation exchange capacity, thus improving its nutrient retention capacity. The potential soil application of ozonized biochar warrants the need for a toxicity study that investigates its effects on microorganisms. Results In the study presented here, we found that the filtrates collected from ozonized pine 400 biochar and ozonized rogue biochar did not have any inhibitory effects on the soil environmental bacteria Pseudomonas putida, even at high dissolved organic carbon (DOC) concentrations of 300 ppm. However, the growth of Synechococcus elongatus PCC 7942 was inhibited by the ozonized biochar filtrates at DOC concentrations greater than 75 ppm. Further tests showed the presence of some potential inhibitory compounds (terephthalic acid and p-toluic acid) in the filtrate of non-ozonized pine 400 biochar; these compounds were greatly reduced upon wet-ozonization of the biochar material. Nutrient detection tests also showed that dry-ozonization of rogue biochar enhanced the availability of nitrate and phosphate in its filtrate, a property that may be desirable for soil application. Conclusion Ozonized biochar substances can support soil environmental bacterium Pseudomonas putida growth, since ozonization detoxifies the potential inhibitory aromatic molecules. Graphical Abstract

Soil Chemical Properties and Fire Severity Assessment Using VNIR Proximal Spectroscopy in Fire-Affected Abandoned Orchard of Mediterranean Croatia

This paper aims to evaluate the ability of VNIR proximal soil spectroscopy to determine post-fire soil chemical properties and discriminate fire severity based on soil spectra. A total of 120 topsoil samples (0–3 cm) were taken from 6 ha of unburned (control (CON)) and burned areas (moderate fire severity (MS) and high fire severity (HS)) in Mediterranean Croatia within one year after the wildfire. Partial least squares regression (PLSR) and an artificial neural network (ANN) were used to build calibration models of soil pH, electrical conductivity (EC), CaCO3, plant-available phosphorus (P2O5) and potassium (K2O), soil organic carbon (SOC), exchangeable calcium (exCa), magnesium (exMg), potassium (exK), sodium (exNa), and cation exchange capacity (CEC), based on soil reflectance data. In terms of fire severity, CON samples exhibited higher average reflectance than MS and HS samples due to their lower SOC content. The PCA results pointed to the significance of the NIR part of the spectrum for extracting the variance in reflectance data and differentiation between the CON and burned area (MS and HS). DA generated 74.2% correctly classified soil spectral samples according to the fire severity. Both PLSR and ANN calibration techniques showed sensitivity to extract information from soil features based on hyperspectral reflectance, most successfully for the prediction of SOC, P2O5, exCa, exK, and CEC. This study confirms the usefulness of soil spectroscopy for fast screening and a better understanding of soil chemical properties in post-fire periods.