The accumulation in soil landfills of toxic and persistent lindane, widely used as an insecticide, triggers the risk of leaching with the concomitant contamination of surrounding rivers. Thus, viable remediation to eliminate in situ high concentrations of lindane in soil and water becomes an urgent demand. In this line, a simple and costeffective composite is proposed, including the use of industrial wastes. It includes reductive and non-reductive base-catalyzed strategies to remove lindane in the media. A mixture of magnesium oxide (MgO) and activated carbon (AC) was selected for that purpose. The use of MgO provides a basic pH. In addition, the specific selected MgO forms double-layered hydroxides in water which permits the total adsorption of the main heavy metals in contaminated soils. AC provides adsorption microsites to hold the lindane and a reductive atmosphere that was increased when combined with the MgO. These properties trigger highly efficient remediation of the composite. It permits a complete elimination of lindane in the solution. In soils doped with lindane and heavy metals, it produces a rapid, complete, and stable elimination of lindane and immobilization of the metals. Finally, the composite tested in lindane-highly contaminated soils permits the in situ degradation of nearly 70% of the initial lindane. The proposed strategy opens a promising way to face this environmental issue with a simple, costeffective composite to degrade lindane and fix heavy metals in contaminated soils.

Humic acids are of great interest in many fields; however, they are inhibitors of fermentative processes applied to hydrothermally treated sewage sludge. Hence, the structure and composition of soluble and bound humic acidlike fractions from raw and hydrothermally treated sewage sludge were studied. Lipid, polysaccharide, protein and aromatic fractions were identified, as well as a high nitrogen content (7-10 %) and low solubility in alkaline media. Thus, they do not strictly meet the chemical definition of 'humic acids'. The soluble humic acid-like compounds had more aromatic and less protein content. Thermal hydrolysis of sewage sludge increased their aromaticity to the detriment of protein and polysaccharide fractions, while wet oxidation caused an increase in all structural fractions. Regarding the bound compounds, lipid, polysaccharide and aromatic fractions increased markedly during both treatments, although oxygen produced higher degradation of the protein fraction and, from 1 h, the partial degradation of aromatic compounds and an increase in the C/N atomic ratio (from 5.0 to 18.7 after 2 h). Therefore, hydrothermal treatments have a positive impact on the hydrolysate biodegradability due to the organic matter solubilisation, but also a negative impact linked to the higher solubilisation of the humic acid-like compounds and their structural changes.

Previous studies have shown that natural heteromolecularcomplexesmight be an alternative to synthetic chelates to correct iron (Fe)deficiency. To investigate the mechanism of action of these complexes,we have studied their interaction with Ca2+ at alkalinepH, Fe-binding stability, Fe-root uptake in cucumber, and chemicalstructure using molecular modeling. The results show that a heteromolecularFe complex including citric acid and lignosulfonate as binding ligands(Ls-Cit) forms a supramolecular system in solution with iron citrateinteracting with the hydrophobic inner core of the lignosulfonatesystem. These structural features are associated with high stabilityagainst Ca2+ at basic pH. Likewise, unlike Fe-EDDHA, rootFe uptake from Ls-Cit implies the activation of the main root responsesunder Fe deficiency at the transcriptional level but not at the post-transcriptionallevel. These results are consistent with the involvement of some plantresponses to Fe deficiency in the plant assimilation of complexedFe in Ls-Cit under field conditions.

Many studies have shown the capacity of soil humic substances (HS) to improve plant growth in natural ecosystems. This effect involves the activation of different processes within the plant at different coordinated molecular, biochemical, and physiological levels. However, the first event triggered by plant root-HS interaction remains unclear. Some studies suggest the hypothesis that the interaction of HS with root exudates involves relevant modification of the molecular conformation of humic self-assembled aggregates, including disaggregation, which might be directly involved in the activation of root responses. To investigate this hypothesis, we have prepared two humic acids. A natural humic acid (HA) and a transformed humic acid obtained from the treatment of HA with fungal laccase (HA enz). We have tested the capacity of the two humic acids to affect plant growth (cucumber and Arabidopsis) and complex Cu. Laccase-treatment did not change the molecular size but increased hydrophobicity, molecular compactness and stability, and rigidity of HA enz. Laccase-treatment avoided the ability of HA to promote shoot- and root-growth in cucumber and Arabidopsis. However, it does not modify Cu complexation features. There is no molecular disaggregation upon the interaction of HA and HA enz with plant roots. The results indicate that the interaction with plant roots induced in both HA and laccase-treated HA (HA enz), changes in their structural features that showed higher compactness and rigidity. These events might result from the interaction of HA and HA enz with specific root exudates that can promote intermolecular crosslinking. In summary, the results indicate that the weakly bond stabilized aggregated conformation (supramolecular-like) of HA plays a crucial role in its ability to promote root and shoot growth. The results also indicate the presence of two main types of HS in the rhizosphere corresponding to those non-interacting with plant roots (forming aggregated molecular assemblies) and those produced after interacting with plant root exudates (forming stable macromolecules).

Phosphate-metal-humic complexes are very relevant in nature due to their crucial role in phosphate availability for plants and microorganisms. Synthetic phosphate-calcium-humic acid (HA) complexes have proven to be efficient sources of available phosphorus for crops. However, the current knowledge about their structure and molecular features is very poor. The structural implications of phosphate interaction with humic binding sites through calcium bridges, in both monocalcium phosphate and dicalcium phosphate is investigated by using molecular modeling, P-31-NMR, H-1-NMR and X-ray diffractometry. The conformational changes in the molecular configuration of the humic acid involved in the interaction resulting from the synthetic process is also studied by using HPSEC and synchronous fluorescence. The results obtained allow us to identify the phosphate type in the crystalline phase that is involved in the interaction of humic acid binding sites and the different forms of calcium phosphate. Synchronous fluorescence also shows that whereas the conformational configuration of the HA binding site is only partially affected in the monocalcium phosphate interaction, it changes in the case of dicalcium phosphate showing simpler molecular arrangements. These changes in the molecular conformation of the binding site in HA in solution may influence the biological activity of the humic acid.

Phosphate fertilizers play an important role in plant nutrition. Different P fertilizer sources such as high-solubility (simple superphosphate, SSP), low-solubility (rock phosphate, RP) and complex superphosphate (CSP) are available for plant supplementation. The objective of this study was to investigate the short- and long-term redistribution of soil P after application of different P sources at establishment of an Eucalyptus forest stand. We carried out two experiments to identify the short- and long- term changes in a Brazilian Oxisol. To property identify the P pools in different times, Hadleýs fractionation methodology was applied to a long-term studies and citrate and oxalate to short-term. From zero to 180 days, the soluble P fractions were not altered in the non-fertilized treatment. Under SSP, a slight increase in this P fraction was found until 30 days, followed by a decrease in later evaluations. During the same period, a slight reduction in Pi extracted by citrate and oxalate was found under the control and a large reduction (approximately 50%) under the SSP treatment. Intermediate behavior was observed under the CSP and RP treatments, whereas there was an increase in P-citrate and P-oxalate until 30 days followed by a reduction afterwards. These results suggest that this pool comprises a potential bioavailability of P to plants.

The ability of rhizospheric humic substances to improve plant growth has been well established by many studies carried out using diverse plant species cultivated under many different conditions. These beneficial effects of humic substances on plant development are expressed in both root and shoot. However, the mechanisms responsible for this action of humic substances are only partially known and poorly integrated. In fact, although the studies focused on plant root development are numerous, those dealing with plant shoot development are scarce. Likewise, studies integrating humic effects on root and shoot are also few. In this context, the main goal of this work is to summarize some of the results regarding the effects of humic substances on plant development within a hypothetical holistic framework that will allow us to interconnect these findings and disclose some features of the functional crosstalk between the effects on soil, root and shoot. Furthermore, the significance of all these mechanisms in plants growing in the field is also discussed.

This study describes the efficiency of a new coating material for preparing granulated potassium-fertilizers with a potassium release to the soil solution sensitive to rainfall intensity. The composite is prepared by reaction of an alkyd-resin with cement in the absence of water. The complementary use of diverse analytical techniques showed that the presence of the cement fraction induced alkyd resin reticulation and gradual cement-resin hardening. Scanning electron microscopy revealed the formation of micro and nanopores within cement-clusters, whose water permeability is affected by the resin reticulation and amphiphilic character. Potassium release was evaluated in water, soil-columns, and in soil-plant trials in pots and open-field. Agronomic results were consistent with potassium release rates obtained in water solution and soil columns. The composite-coated potassium fertilizer was more efficient than the noncoated one in providing plant available potassium, with this effect being dependent on water presence in soil.

The aim of this review is to describe the main physicochemical characteristics of diverse typesof humic-metal-phosphate acid complexes. The effects of these complexes on phosphorus (P)fixation in soils with different pH values and physicochemical features and on plant phosphorusuptake are also discussed. Humic-metal-phosphate complexes have apparent stability con-stants in the same range as those of metal-humic complexes, in solutions with diverse pH andionic-strength values. Likewise, the molecular-size distribution of humic-metal-phosphate com-plexes as a function of pH is similar to that of potassium or sodium humates and metal-humiccomplexes. Humic-metal-phosphate complexes are able to decrease phosphate fixation in soilsand increase plant growth and phosphate uptake. Phosphorus fertilizers containing humic-metal-phosphate complexes proved to be efficient to improve plant growth and P uptake withrespect to conventional fertilizers such as single superphosphate. The values of parametersrelated to plant phosphorus-utilization efficiency (PUt E) suggest that the regulation of rootacquisition of phosphate from these complexes could involve the interregulation of a system forthe optimization of metabolic P utilization in the shoot and another system involving stressresponses of roots under phosphorus deficiency.

Fertilizers based on phosphate-metal-humate complexes are a new family of compounds that represents a more sustainable and bioavailable phosphorus source. The characterization of this type of complex by using solid (31)P NMR in several fertilizers, based on single superphosphate (SSP) and triple superphosphate (TSP) matrices, yielded surprising and unexpected trends in the intensity and fine structure of the (31)P NMR peaks. Computational chemistry methods allowed the characterization of phosphate-calcium-humate complexes in both SSP and TSP matrices, but also predicted the formation of a stable sulfate-calcium-humate complex in the SSP fertilizers, which has not been described previously. The stability of this complex has been confirmed by using ultrafiltration techniques. Preference towards the humic substance for the sulfate-metal phase in SSP allowed the explanation of the opposing trends that were observed in the experimental (31)P NMR spectra of SSP and TSP samples. Additionally, computational chemistry has provided an assignment of the (31)P NMR signals to different phosphate ligands as well as valuable information about the relative strength of the phosphate-calcium interactions within the crystals.

The role of soil humus in soil fertility and crop production has been well established by many studies and practical farming experience. This role is related to the presence of a family of organic substances, known as humic substances, with the capacity to increase the pool of plant-available nutrients in soil for root uptake. The improvement in plant growth and mineral nutrition is directly linked to the physicochemical features of humic substances, and more specifically, to their capacity to form stable chemical complexes with metals. This chapter reviews the main mechanisms behind the action of humic substances in improving plant mineral nutrition. It also discusses the main signalling pathways that might be involved in the regulation of these humic substances.