Potential of Biochar from Wood Gasification to Retain Endocrine Disrupting Chemicals.

In this study, a biochar obtained from poplar wood gasification at a temperature of 850 °C was used to adsorb the xenoestrogens 4-tert-octylphenol (OP) and bisphenol A (BPA) and the herbicide metribuzin from water. Scanning electron microscopy (SEM-EDX) and Fourier-transform infrared (FTIR) spectroscopy were employed to investigate the surface micromorphology and functional groups composition of biochar, respectively. The study of sorption kinetics showed that all compounds achieved the steady state in less than 2 h, according to a pseudo-second order model, which denoted the formation of strong bonds (chemisorption) between biochar and the compounds. Adsorption isotherms data were described by the Henry, Freundlich, Langmuir and Temkin equations. At temperatures of 10 and 30 °C, the equilibrium data of the compounds were generally better described by the Freundlich model, although, in some cases, high correlation coefficients (r ≥ 0.98) were obtained for more than one model. Freundlich constants, KF, for OP, BPA and metribuzin were, respectively, 218, 138 and 4 L g-1 at 10 °C and 295, 243 and 225 L g-1 at 30 °C, indicating a general increase of adsorption at higher temperature. Desorption of all compounds, especially OP and BPA, from biochar was slow and very scarce, denoting an irreversible and hysteretic process. Comparing the results of this study with those reported in the literature, we can conclude that the present biochar has a surprising ability to retain organic compounds almost permanently, thus behaving as an excellent low-cost biosorbent.

Phytotoxic metabolites produced by Verticillium dahliae Kleb. in olive wilting: a chemical and spectroscopic approach for their molecular characterisation.

Most of the symptoms associated with Verticillium wilt disease in olive cultivation are due to complexes excreted by Verticillium dahliae. In this study chemical and physico-chemical techniques were combined to investigate how the molecular structure of phytotoxins isolated from two pathotypes of Verticillium dahliae, defoliating, D, and non-defoliating, ND, grown on two different media, Verticillium-dahliae-Medium (VdM) and Simulated Xylem-fluid-Medium (SXM), can affect their aggressiveness. Data obtained highlight important structural differences, both in term of elemental composition and in functional groups distribution. Such peculiarities strongly affect their solubility, resulted higher for the phytotoxins from D pathotype. This property likely induces serious modifications of the conformational state of the proteinaceous component, making tyrosine residues accessible to the phosphate ion. A phosphorylation mechanism would thus be promoted, that is going to interfere with the function of the involved proteins in intracellular signalling networks, likely by altering its role in modulating the plant's response.

Biochar effect on crop performance and Pb and Zn uptake of tomato (Solanum lycopersicum, L.) plants grown on heavy metals contaminated Kosovo soils.

A greenhouse pot experiment was conducted to evaluate the effect of biochar on the growth and uptake of Pb and Zn by tomato plants (Solanum lycopersicum, L.) cultivated in two highly contaminated Kosovo soils, A and B. Plants were cultivated in the biochar amended and unamended soils. As expected, the biochar addition to the two polluted soils has contributed to significantly improve the crop yields, in terms of both fresh and dry weight. Further, results indicated that the effect of biochar on metal mobility is closely related, besides its properties, to soil's native characteristics. In fact, the addition of biochar to soil B had also beneficial effects on the uptake of both metals, halving in some cases the values of the biological accumulation and transfer coefficients, while it did not show the same efficacy on soil A.

Wood biochars and vermicomposts from digestate modulate the extent of adsorption-desorption of the fungicide metalaxyl-m in a silty soil.

This study aimed to investigate changes in metalaxyl-M sorption-desorption capacity of soil following the addition of two types of amendments. Two biochars (BC) from grapevine pruning residues (BC-G) and spruce wood (BC-S) and two vermicomposts (VC) obtained vermicomposting digestates from a mixture of manure and olive mill wastewater (VC-M) and buffalo manure (VC-B) were used. Using a batch equilibration method, the materials and a silt loam soil non-amended or amended with each material at 2% (w/w) were interacted with the fungicide at a concentration of 2 mg L-1 for kinetics study and in the range 1-20 mg L-1 for sorption isotherms. Kinetics results showed that metalaxyl-M onto the amendments and non-amended soil followed preferentially a pseudo-second-order model, thus indicating a chemisorption process. Sorption isotherm data of the product on BC and VC fitted well the Freundlich equation, whereas those on non-amended and amended soil followed preferentially a linear model. The KFads values were 995.2, 788.5, 55.2, 52.1, 6.4, 6.0, 3.4, 2.6 and 1.5 L kg-1 for BC-G, BC-S, VC-M, VC-B, soil-BC-G, soil-BC-S, soil-VC-M, soil-VC-B and non-amended soil, respectively. Product desorption from each soil sample occurred to a lesser extent than sorption. Highly significant correlations (P < 0.005) were found between the values of sorption and desorption constants of all adsorbents and organic C content, thus confirming the prominent role of organic matter in the sorption process of metalaxyl-M.

Insight into the interaction mechanism of iron ions with soil humic acids. The effect of the pH and chemical properties of humic acids.

The main aim of this work was to study the mechanisms of interaction between iron(II) ions and humic acids as a function of pH, iron concentration and various humic acids chemical properties, including the degree of humification, elemental composition, aromaticity and content of acidic functional groups. The results indicated that iron was bound by humic acids at pH 7 in amounts ∼2 times higher than at pH 5 (averaged capacities: 117 and 57 cmol/kg, respectively). Iron binding at pH 7 increased with increasing the total carboxylic and phenolic groups content and the degree of humification of humic acids (R-coefficients: 0.99 and 0.95, respectively). The stability of humic acid-iron complexes at pH 7 were only slightly lower than at pH 5 due to iron hydroxides formed at pH > 5 (averaged stability constants: 5.18 and 5.26, respectively). Iron coordination mode varied depending on pH: at pH 5, the bidentate (chelate) mode dominated, whereas at pH 7 the bridging mode appeared prevalent. The total amount of bound iron was much smaller than the content of the carboxylic and phenolic groups in humic acids, on average by ∼80 (pH 7) and ∼90.1% (pH 5) indicating the occurrence of steric effects in humic acid structure i.e. the reduction of the complexation capacity of free functional groups by adjacent groups occupied by iron and/or the formation of intramolecular aggregates with iron hindering the access of further metal ions. At pH 5 the complexes were soluble in the iron concentration range positively correlated to carboxylic and phenolic groups content, showing the protective nature of negatively charged functional groups on the stability of the solution. At this pH, the destabilization of the system was governed by the neutralization of humic acid charged structures by metal cations and the compression of the double electric layer. At pH 7 the stability of the humic acid-iron solution was largely determined by the form of iron, mainly by the precipitation of metal hydroxides acting as a flocculant destabilizing the solution by co-precipitation of humic acid-iron complexes.

Methylated arsenic species throughout a 4-m deep core from a free-floating peat island.

Arsenic (As) occurs in soils mostly in inorganic forms, whereas the organic forms usually occur only in trace amounts. Peatlands are waterlogged, generally anoxic, organic soils representing the first step in coal formation; the contribution of organic vs. inorganic As species in this environment has received little research attention. Here, 57 peat samples collected throughout a 4-m deep, free-floating mire were analysed for total As and for its organic species, including dimethylarsinic acid (DMA), methylarsonic acid (MA), trimethylarsine oxide (TMAO) and arsenobetaine (AB), by HPLC-ICPMS. Aqueous trifluoroacetic acid was used as extractant, resulting in an average extraction efficiency of almost 80%. Total As concentration throughout the profile ranged between 0.2 and 9.8mg/kgpeat (mean: 1.4±1.2mg/kgpeat). Organic As species (DMA+MA+TMAO+AB) accounted, on average, for 28±10% of total As (range: 6-51%), and for 37±13% of the extracted As (range: 7-64%). The relative abundance of organoarsenicals generally followed the order DMA>TMAO~MA≫AB. A positive correlation (p<0.001) was found among all organic As compounds, whereas their concentrations were negatively correlated with total sulfur content. The submerged zone (bottom 300cm) showed average and maximum concentrations of organoarsenic compounds that were almost twice those found in the top 100cm. This study shows that significant proportions of methylated As species occur even in peat samples characterized by low total As concentration (mostly <2mg/kg). Finally, this work provides the first evidence of organoarsenic species in free-floating mires, i.e., a globally distributed but scarcely investigated ecosystem.

Rapid peat accumulation favours the occurrence of both fen and bog microbial communities within a Mediterranean, free-floating peat island.

The unique environment of a 4m-thick, free-floating peat island within the Posta Fibreno lake (Central Italy) was analyzed using DNA-based techniques to assess bacterial and fungal community members identity and abundance. Two depths were sampled at 41 and 279 cm from the surface, the former corresponding to an emerged portion of Sphagnum residues accumulated less than 30 yrs ago, and the latter mainly consisting of silty peat belonging to the deeply submerged part of the island, dating back to 1520-1660 AD. The corresponding communities were very diverse, each of them dominated by a different member of the Delta-proteobacteria class for prokaryotes. Among Eukaryotes, Ascomycota prevailed in the shallow layer while Basidiomycota were abundant in the deep sample. The identity of taxa partitioning between acidic surface layer and neutral core is very reminiscent of the differences reported between bogs and fens respectively, supporting the view of Posta Fibreno as a relic transitional floating mire. Moreover, some microbial taxa show an unusual concurrent species convergence between this sub-Mediterranean site and far Nordic or circumpolar environments. This study represents the first report describing the biotic assemblages of such a peculiar environment, and provides some insights into the possible mechanisms of its evolution.

Highly anomalous accumulation rates of C and N recorded by a relic, free-floating peatland in Central Italy.

Floating islands mysteriously moving around on lakes were described by several Latin authors almost two millennia ago. These fascinating ecosystems, known as free-floating mires, have been extensively investigated from ecological, hydrological and management points of view, but there have been no detailed studies of their rates of accumulation of organic matter (OM), organic carbon (OC) and total nitrogen (TN). We have collected a peat core 4 m long from the free-floating island of Posta Fibreno, a relic mire in Central Italy. This is the thickest accumulation of peat ever found in a free-floating mire, yet it has formed during the past seven centuries and represents the greatest accumulation rates, at both decadal and centennial timescale, of OM (0.63 vs. 0.37 kg/m2/yr), OC (0.28 vs. 0.18 kg/m2/yr) and TN (3.7 vs. 6.1 g/m2/yr) ever reported for coeval peatlands. The anomalously high accretion rates, obtained using 14C age dating, were confirmed using 210Pb and 137Cs: these show that the top 2 m of Sphagnum-peat has accumulated in only ~100 years. As an environmental archive, Posta Fibreno offers a temporal resolution which is 10x greater than any terrestrial peat bog, and promises to provide new insight into environmental changes occurring during the Anthropocene.

Chemical and spectroscopic characteristics of humic acids and dissolved organic matter along two Alfisol profiles.

The aim of this study was to elucidate the heterogeneous structural and functional composition of humic acids (HAs) and dissolved organic matter (DOM) isolated from two Alfisol profiles with different soil texture, in order to develop a better understanding of the organic matter dynamics. Soil samples were collected at different depths from three (Ap, 2AB and 2Bt) and eight (A1, A2, A3, E1, E2, 2Bt1, 2Bt2 and 2Bt3) soil horizons of two Alfisols located in the south (PR1) and north (PR2) of Italy, with a clay texture and a silt loam to loam ones, respectively. Chemical and spectroscopic methods were used to characterize the HAs and the DOM isolated from different soil horizons, including Ultraviolet-Visible (UV-Vis), Fourier Transform Infrared (FTIR), and Fluorescence spectroscopies. The HAs and the DOM isolated from the two Alfisols apparently showed significant differences in their compositional, structural and functional characteristics. In particular, the HAs isolated from the PR1 featured a higher degree of humification and molecular complexity with respect to those isolated from the PR2. On the contrary, the DOM samples isolated from the PR2 showed a more marked aromatic character and polycondensation degree. Both the HAs and the DOM obtained from the PR1 presented a greater qualitative homogeneity with respect to those obtained from the PR2. These results could be reasonably ascribed to the different texture and horizons of the two Alfisols, and to a greater pedogenesis occurred in the PR1.

Interactions between rotenone and humic acids by means of FT-IR and fluorescence spectroscopies.

The aim of this work was to ascertain, on a comparative basis, the compositional, structural and functional differences occurring between three humic acids (HAs), HA S1 (isolated from a Mediterranean brown soil), HA S2 (isolated from a Bavarian brown soil), and HA SR (a Suwannee River standard aquatic HA, purchased from IHSS), and to investigate the influence of their intrinsic properties on the types of binding mechanisms toward the pesticide rotenone. Original HAs and their corresponding HA-rotenone products, obtained by two different interaction protocols, were analyzed for elemental and functional group composition, and spectroscopic techniques, such as Fourier-transform infrared (FT IR) with Fourier self-deconvolution (FSD) and fluorescence both in the single-scan and in three-dimensional modes. The HA S1 sample appeared to be characterized by a greater aromaticity degree and lower polarity with respect to the HA S2, featured by a mixed aromatic/aliphatic character, whereas mainly aliphatic and acidic resulted the HA SR. The data obtained suggested that the low water-soluble, non-polar pesticide rotenone resulted preferentially adsorbed onto HAs by hydrophobic interaction, that was the prevailing mechanism in the order HA S1 > HA S2 >>> HA SR, whereas hydrogen bonds resulted predominant in the opposite order.

Elemental and spectroscopic characterization of humic-acid-like compounds during composting of olive mill by-products.

Humic acids (HAs) were isolated at different stages of composting from two piles of solid olive mill residues (SOR) treated for the first 30 days with tap water (pile C1) or olive mill wastewater (pile C2), for a total composting period of 9 months. The HA fractions were characterized by elemental analysis, UV-visible, Fourier transform infrared and fluorescence spectroscopy in order to monitor humification process and the maturity of the composts. As composting proceeded, the elemental composition of the humic acids showed a decrease in C and H content, and in the C/N ratio, and an increase in N and O contents and in the C/H and O/C ratios. These changes could be attributed to a loss of aliphatic groups and to an increase of aromatic character, polycondensation and degree of oxidation of the HAs. Spectroscopic data agree and support these results, suggesting that the chemical and structural features of the HAs of both composts tend to reach those typical of native soil HAs, that is compounds with a high degree of humification and a high molecular weight and complexity. Therefore, both composting processes seem suitable to produce well-humified organic matter, with important benefits for their use in soil amendment. No differences appeared between the two treatments concerning the humic character of the two final composts.

Study of the biodegradation and transformation of olive-mill residues during composting using FTIR spectroscopy and differential scanning calorimetry.

The aim of this work was to investigate the structural transformations occurring in organic matter and their relationships with organic matter stability during the composting of two different solid olive-mill residues (SOMR). Raw materials were prepared from SOMR (compost C1) and from a mixture of SOMR and olive-mill wastewater for compost C2. Composts evolution was monitored by direct Fourier transform infra-red (FTIR) spectroscopy and differential scanning calorimetry (DSC) and by physicochemical parameters. Results showed that both wastes are suitable for composting and showed a strong thermophilic phase extending over the first 2 months, progressively and slowly reaching maturity after approximately 6 months. By the end of the thermophilic phase the water-soluble phenol content decreased by 93% and the pH and organic matter loss became more stable, oscillating around 8.5 and 41%, respectively. DSC and FTIR results showed that the biodegradation of the heterogeneous raw material is progressive and can be mainly attributed to a loss of aliphatic and peptidic structures and to an increase of the aromatic structures which essentially occurs during the maturity phase. By the end of the maturity phase, the two composts showed DSC and FTIR spectra typical of humic-like substances confirming the high degree of humification of the end products.

Characterization of water extractable organic matter in a deep soil profile.

The aim of this study was to identify qualitative and quantitative differences of water extractable organic matter (WEOM) isolated from each horizon along a deep soil profile and to evaluate any relationship between the WEOC and the total organic carbon (TOC) content. The soil profile "Monte Pietroso" is located in the Murge area, Apulia region in Southern Italy. Samples from the eight horizons (Ap1, Ap2, Ab1, Ab2, Bt1, 2B, 2Bt2, and 2B/C) were collected in October 2002. The WEOM characterization was carried out by means of UV absorbance, fluorescence spectroscopy in the emission and excitation/emission matrix (EEM) modes, and additional spectroscopic derived indexes. Soil organic carbon was shown to accumulate in the top horizons (Ap) and, in general, to decrease with depth, whereas, the WEOM/TOC ratio increases with increasing depth. The aromaticity and the humification index of the WEOM decrease dramatically downward the soil profile, whereas the fluorescence efficiency index tends to increase markedly. The WEOM fractions feature three main fluorophores with different wavelength and relative intensity. In general WEOM transport phenomena are suggested to occur downward the soil profile, depending on the nature of the organic material and on the chemical and mineral characteristics of the various horizons.

Spectroscopic and thermal investigations on compost improved by iron salt addition.

A quality compost obtained from sewage sludge (one part in weight) and yard trimmings and sawdust (two parts) has been investigated as a potential carrier of iron to plants. At the end of the thermophilic phase, the composting materials were added with crystalline FeSO4.7H2O (97%). Chemical properties, respiratory indices, and seed germination tests proved the compost to be suitable as an iron carrier in agriculture. Fourier transform infrared spectroscopy (FT-IR) and fluorescence spectroscopy provided evidence of the effective linking of the iron ion to the organic molecule functional groups, thus preventing the loss of iron ion by leaching and precipitation phenomena and allowing the metal ion to be available to plants as both mineral and organic species. The thermogram obtained on compost without iron was similar to that previously obtained for composted materials of different origins, whereas samples with added iron ion exhibited in addition an exotherm in the medium-temperature region. FT-IR spectra carried out on samples heated at different temperatures indicated a loss of iron ion linked to carboxyl groups.

Fluorescence behaviour of Zn and Ni complexes of humic acids from different sources.

Conventional fluorescence spectroscopy in the excitation, emission and synchronous scan modes and three-dimensional fluorescence spectroscopy in the form of an excitation-emission matrix (EEM) of fluorescence intensity as a function of excitation and emission wavelengths have been applied to the study of three humic acids (HAs) extracted from soil (SHA), peat (PHA) and compost (CHA) and their interaction products with Zn(II) and Ni(II) ions. Fluorescence spectra of HAs appear to be related to the nature and origin of the sample. A strong reduction of intensity of all peaks is observed in the spectra of HAs-metal complexes as compared to those of untreated HAs. Ni(II) exhibits greater quenching ability than Zn(II). Fluorescence quenching measured for complexes of HAs at increasing Ni(II) concentrations was linearly correlated with metal ion concentration. The different capacity to interact with metal ions showed by various HAs is attributed to their different molecular complexity.

Effects of pig slurry application on soils and soil humic acids.

The effect of three annually consecutive additions of pig slurry at two rates (90 and 150 m3 x ha(-1) x year(-1) on soils and soil humic acids (HAs) was investigated in a field experiment under semiarid conditions. Soils and pig slurries were analyzed by standard methods. The HAs were isolated from soils and pig slurry by a conventional procedure based on alkaline extraction, acidic precipitation to pH 1, purification by repeated alkaline dissolutions and acidic precipitations, water washing, dialysis, and final freeze-drying. The HAs obtained were analyzed for elemental (C, H, N, S, and O) and acidic functional group (carboxylic and phenolic) composition, and by UV-vis, FT-IR, fluorescence, and ESR spectroscopies. With respect to the control soil, the pig slurry amended soils had greater pH and electrical conductivity, slightly larger total N content, and smaller values of C/N ratio. A decrease of total organic C was observed only in soils amended for 2 and 3 years at the higher slurry rate. With respect to control soil HA, pig slurry HA was characterized by larger contents of S- and N-containing groups, smaller acidic functional group and organic free radical contents, a prevalent aliphatic character, extended molecular heterogeneity, and smaller aromatic polycondensation and humification degrees. Amendment with pig slurry HA determines a number of modifications in soil HAs, including increase of C, S, and COOH contents, C/N ratios, and aliphaticity and decrease of extraction yields and N, O, phenolic OH, and organic free radical contents. These effects are generally more evident after the first year of slurry application and tend to disappear with increasing number of treatments. Most probably, over the years the slightly humified slurry HA is mineralized through extended microbial oxidation, whereas only the most recalcitrant components, such as S-containing, phenolic, and aliphatic structures, are partially accumulated by incorporation into soil HA.