Vincenza Cozzolino

Sorption/desorption of arsenate on/from Mg–Al layered double hydroxides: Influence of phosphate

We have studied: (i) the sorption of arsenate on Mg-Al layered double hydroxides (LDHs) containing chloride (LDH-Cl) or carbonate (LDH-CO(3)) in the absence or presence of phosphate; (ii) the competitive sorption of arsenate and phosphate as affected by reaction time and pH and; (iii) the desorption of arsenate previously sorbed on the LDH by phosphate. The LDH samples were uncalcined (LDH-Cl-20 and LDH-CO(3)-20) or calcined at 450 degrees C (LDH-Cl-450 and LDH-CO(3)-450). More phosphate than arsenate was sorbed onto all the minerals but LDH-Cl-450 sorbed much lower amounts of both the ligands than LDH-Cl-20; vice versa LDH-CO(3)-450 showed a capacity to sorb arsenate and phosphate much greater than LDH-CO(3)-20. XRD analysis showed that arsenate was included into the layer spaces of LDH-Cl-20, but not in those of LDH-CO(3)-20. Competition in sorption between arsenate and phosphate was affected by pH, reaction time, surface coverage and sequence of addition of the ligands. Phosphate showed a greater affinity for LDHs than arsenate. The final arsenate sorbed/phosphate sorbed molar ratio increased with reaction time or by adding arsenate before phosphate, but decreased by increasing pH and by adding phosphate before arsenate. The effect of reaction time on the desorption of arsenate by phosphate was also studied.

Sorption of arsenite and arsenate on ferrihydrite: Effect of organic and inorganic ligands

We studied the sorption of As(III) and As(V) onto ferrihydrite as affected by pH, nature and concentration of organic [oxalic (OX), malic (MAL), tartaric (TAR), and citric (CIT) acid] and inorganic [phosphate (PO(4)), sulphate (SO(4)), selenate (SeO(4)) and selenite (SeO(3))] ligands, and the sequence of anion addition. The sorption capacity of As(III) was greater than that of As(V) in the range of pH 4.0-11.0. The capability of organic and inorganic ligands in preventing As sorption follows the sequence: SeO(4) ≈ SO(4) < OX < MAL ≈ TAR < CIT < SeO(3) ≪ PO(4). The efficiency of most of the competing ligands in preventing As(III) and As(V) sorption increased by decreasing pH, but PO(4) whose efficiency increased by increasing pH. In acidic systems all the competing ligands inhibited the sorption of As(III) more than As(V), but in alkaline environments As(III) and As(V) seem to be retained with the same strength on the Fe-oxide. Finally, the competing anions prevented As(III) and As(V) sorption more when added before than together or after As(III) or As(V).

Sorption of Cu, Pb and Cr on Na-montmorillonite: competition and effect of major elements.

The competitive sorption among Cu, Pb and Cr in ternary system on Na-montmorillonite at pH 3.5, 4.5 and 5.5 and at different heavy metal concentrations, and the effect of varying concentrations of Al, Fe, Ca and Mg on the sorption of heavy metals were studied. Competitive sorption of Cu, Pb and Cr in ternary system on montmorillonite followed the sequence of Cr≫Cu>Pb. Moreover, the competition was weakened by the increase of pH while was intensified by the increase of heavy metal concentration. The sorption of heavy metal on montmorillonite was inhibited by the presence of Ca and Mg, while Al and Fe showed different patterns in affecting heavy metal sorption. Aluminum and Fe generally inhibited the sorption of heavy metal when the pH and/or concentration of major elements were relatively low. However, promoting effects on heavy metal sorption by Al and Fe were found at relatively high pH and/or great concentration of major elements. The inhibition of major elements on heavy metal sorption generally followed the order of Al>Fe>Ca⩾Mg, while Fe was more efficient than Al in promoting the sorption of heavy metals. These findings are of fundamental significance for evaluating the mobility of heavy metals in polluted environments.

Effect of inorganic and organic ligands on the sorption/desorption of arsenate on/from Al-Mg and Fe-Mg layered double hydroxides.

This paper describes the sorption of arsenate on Al-Mg and Fe-Mg layered double hydroxides as affected by pH and varying concentrations of inorganic and organic ligands, and the effect of residence time on the desorption of arsenate by ligands. The capacity of ligands to inhibit the fixation of arsenate followed the sequence: nitrate<nitrite<sulphate<selenite<tartrate<oxalate≪phosphate on Al-Mg-LDH and nitrate<sulphate≈nitrite<tartrate<oxalate<selenite≪ phosphate on Fe-Mg-LDH. The inhibition of arsenate sorption increased by increasing the initial ligand concentration and was greater on Al-Mg-LDH than on Fe-Mg-LDH. The longer the arsenate residence time on the LDH surfaces the less effective the competing ligands were in desorbing arsenate from sorbents. A greater percentage of arsenate was removed by phosphate from Al-Mg-LDH than from Fe-Mg-LDH, due to the higher affinity of arsenate for iron than aluminum.

The molecular characteristics of compost affect plant growth, arbuscular mycorrhizal fungi, and soil microbial community composition

Compost amendment to agricultural soils influences plant growth and soil quality by affecting activity of arbuscular mycorrhizal fungi (AMF) and composition of microbial community. We related the molecular composition of compost of different maturity added to soils to their effects on maize growth, N and P uptake, AMF root colonization and growth, and composition of soil microbial community. The characteristics of compost after different days of maturation (C60, C90, C120) were provided by 13C-solid state NMR spectroscopy, while neutral (NLFA) and phospholipid (PLFA) fatty acid analyses were used to evaluate the effects of compost on the composition of soil microbial communities. Multivariate elaboration was used to determine the relationships between microbial groups, as identified by PLFA analysis, and molecular properties of composts. Although compost amendments increased soil total C and N, and available P, soil addition of both C60 and C120 compost samples was detrimental to plant and AMF growth. Compost amendments modified the composition of soil microbial communities. The high content of biolabile compounds in C60 and C120 compost samples decreased the C16:1ω5 NLFA that was related to AMF and Gram(+)/Gram(−) and AMF/saprotrophic fungi ratios. A linear correlation was found between the molecular indexes in compost and the microbial groups in soil, thereby suggesting that the molecular composition of compost strictly controls the development and abundance of soil microbial communities. These findings highlight the importance of controlling the molecular quality of recycled biomass added to soil, in order to predict the effect on crop yields and biotic composition of soil.

Molecular evaluation of soil organic matter characteristics in three agricultural soils by improved off-line thermochemolysis: the effect of hydrofluoric acid demineralisation treatment.

The molecular composition of soil organic matter (SOM) in three agricultural fields under different managements, was evaluated by off-line thermochemolysis followed by gas chromatography mass spectrometry analysis (THM-GC-MS). While this technique enabled the characterization of SOM components in coarse textured soil, its efficiency in heavy textured soils was seriously affected by the interference of clay minerals, which catalyzed the formation of secondary artifacts in pyrolysates. Soil demineralization with hydrofluoric acid (HF) solutions effectively improved the reliable characterization of organic compounds in clayey soils by thermochemolysis, while did not alter significantly the results of coarse textured soil. A wide range of lignin monomers and lipids molecules, of plant and microbial origin, were identified in the pyrograms of HF treated soils, thereby revealing interesting molecular differences between SOM management practices. Our results indicated that clay removal provided by HF pretreatment enhanced the capacity of thermochemolysis to be a valuable and accurate technique to study the SOM dynamics also in heavy-textured and OC-depleted cultivated soils.

Higher sorption of arsenate versus arsenite on amorphous Al-oxide, effect of ligands

Arsenic pollution is currently a major health issue because As is toxic for human beings, animals, and plants. Knowledge of As mobility is therefore important to assess health risk. The sorption of arsenite and arsenate on metal oxides in the presence of various anionic ligands is closely linked to the mobility, bioavailability, and risk. It was reported that the sorption mechanisms and characteristics of arsenite and arsenate on Al-oxides were different from that on Fe-oxides. Previous work reports the sorption of arsenite and arsenate on Fe-oxides in the presence of ligands. Whereas there is few knowledge on the sorption of arsenite and arsenate by Al-oxides in the presence of ligands. Here, we studied the sorption of arsenite and arsenate on amorphous Al-oxide by batch experiments. We tested the effect of organic ligands: oxalate, malate, tartrate, citrate; and inorganic ligands: sulfate, phosphate, selenate, selenite. Results show that amorphous Al-oxide has more sorption affinity for arsenate than arsenite. The inhibition of As sorption by ligands at pH 6 is higher for arsenite than arsenate. For arsenite, the As sorption inhibition decreases in the order phosphate, citrate, malate, selenite, oxalate, tartrate, sulfate, and selenate. For arsenate, the As sorption inhibition decreases in the order phosphate, malate, citrate, selenite, tartrate, oxalate, sulfate, and selenate.

Potential of three microbial bio-effectors to promote maize growth and nutrient acquisition from alternative phosphorous fertilizers in contrasting soils

BackgroundAgricultural production is challenged by the limitation of non-renewable resources. Alternative fertilizers are promoted but they often have a lower availability of key macronutrients, especially phosphorus (P). Biological inoculants, the so-called bio-effectors (BEs), may be combined with these fertilizers to improve the nutrient use efficiency.MethodsThe goal of this study was to assess the potential of three BEs in combination with alternative fertilizers (e.g., composted manure, biogas digestate, green compost) to promote plant growth and nutrient uptake in soils typical for various European regions. Pot experiments were conducted in Czech Republic, Denmark, Germany, Italy, and Switzerland where the same variety of maize was grown in local soils deficient in P in combination with alternative fertilizers and the same set of BEs (Trichoderma, Pseudomonas, and Bacillus strains). Common guidelines for pot experiment implementation and performance were developed to allow data comparison, and soils were analyzed by the same laboratory.ResultsEfficiency of BEs to improve maize growth and nutrient uptake differed strongly according to soil properties and fertilizer combined. Promising results were mostly obtained with BEs in combination with organic fertilizers such as composted animal manures, fresh digestate of organic wastes, and sewage sludge. In only one experiment, the nutrient use efficiency of mineral recycling fertilizers was improved by BE inoculation.Conclusions These BE effects are to a large extent due to improved root growth and P mobilization via accelerated mineralization.Graphical abstractPossible modes of action of bio-effectors.

Water-soluble lignins from different bioenergy crops stimulate the early development of maize (Zea mays, L.).

The molecular composition of water-soluble lignins isolated from four non-food bioenergy crops (cardoon CAR, eucalyptus EUC, and two black poplars RIP and LIM) was characterized in detail, and their potential bioactivity towards maize germination and early growth evaluated. Lignins were found to not affect seed germination rates, but stimulated the maize seedling development, though to a different extent. RIP promoted root elongation, while CAR only stimulated the length of lateral seminal roots and coleoptile, and LIM improved only the coleoptile development. The most significant bioactivity of CAR was related to its large content of aliphatic OH groups, C-O carbons and lowest hydrophobicity, as assessed by 31P-NMR and 13C-CPMAS-NMR spectroscopies. Less bioactive RIP and LIM lignins were similar in composition, but their stimulation of maize seedling was different. This was accounted to their diverse content of aliphatic OH groups and S- and G-type molecules. The poorest bioactivity of the EUC lignin was attributed to its smallest content of aliphatic OH groups and largest hydrophobicity. Both these features may be conducive of a EUC conformational structure tight enough to prevent its alteration by organic acids exuded from vegetal tissues. Conversely the more labile conformational arrangements of the other more hydrophilic lignin extracts promoted their bioactivity by releasing biologically active molecules upon the action of exuded organic acids. Our findings indicate that water-soluble lignins from non-food crops may be effectively used as plant biostimulants, thus contributing to increase the economic and ecological liability of bio-based industries.

Optimized procedure for the determination of P species in soil by liquid-state 31 P-NMR spectroscopy

BackgroundLiquid-state 31P-NMR spectroscopy becomes progressively an important role for studying phosphorus (P) dynamics in soil. Soils of different origin and organic matter content were used to optimize sample preparation and re-dissolution procedures to improve characterization of P species in soil by 31P-NMR spectroscopy. The efficiency of P extraction from an untreated fresh soil was compared to that from freeze-dried and air-dried soil samples.ResultsA freeze-drying pretreatment not only provided the greatest extraction yields of total and organic P from both farmland and forest soils but also enhanced the intensity of signals for inorganic and organic P species in 31P-NMR spectra, except for polyphosphates. Re-dissolution of freeze-dried soil extracts in relatively dilute alkaline solution and addition of a small aliquot of concentrated HCl to the NMR tube prior to analysis improved the quality of NMR spectra. Finally, the visibility of relatively weak P signals, such as for phosphorus diesters, phosphonates, polyphosphate, phospholipids, and DNA were reproducibly enhanced when 31P-NMR spectra were generated after at least 15 h of acquisition time.ConclusionThe optimized procedure presented here ensured the greatest detectability of inorganic and organic P species by liquid-state P-NMR spectroscopy in soil extracts.