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Effect of the nature of exogenous organic matter on pesticide sorption by the soil.

A study was carried out on the sorption of two sparingly water-soluble pesticides (diazinon and linuron) by a sandy loam soil modified with different exogenous organic materials (EOMs) containing humic-like substances: city refuse compost (CRC), peat (P), commercial "humic" acid (HA), liquid "humic" acid (LHA), and two (nonhumic) model compounds (surfactants), tetradecyltrimethylammonium bromide (TDTMA) and sodium dodecyl sulphate (SDS), before and after 2- and 8-month incubation periods with the soil. In all cases, the isotherms fitted the Freundlich sorption equation (x/m = KCen), generally with r2 values greater than 0.99. The value of the sorption constant K for the natural soil was 8.81 for diazinon and 2.29 for linuron. These values increased significantly for EOM modified soils with respect to natural soil, with the exception of the samples modified with SDS and LHA, in which cases they decreased, possibly due to the micellar properties of these compounds. Incubation of EOMs with soil increased their sorption capacity: the Koc values were increased proportionally to the incubation time for both pesticides and for all treatments carried out. Accordingly, the sorption capacity of hydrophobic pesticides increases with the degree of evolution in the soil of EOMs with "humic"-type compounds, possibly due, among other causes, to the increase in the EOMs' colloidal properties and the modifications occurring in the hydrophobic-hydrophilic characteristics of the soil surfaces. The main conclusion is that application to the soil of carbon-rich wastes, especially those with a high degree of maturity, may offer an important strategy for reducing pesticide leaching and for eliminating pesticide residues from soil with the use of anionic surfactants.

Adsorption↗

Microbial utilization and transformation of humic acid-like substances extracted from a mixture of municipal refuse and sewage sludge disposed of in a landfill.

The purpose of the research was to establish whether humic acid-like substances (HA) related to municipal refuse disposed of in a landfill can resist microbial degradation and if they contribute, in that way, to long-term stabilization of landfill refuse. Using a mixture of 0.1 M Na(4)P(2)O(7) + 0.1 M NaOH, we extracted HA from municipal refuse mixed with sewage sludge and disposed of for up to 12 months, in a 40-m(3) model landfill. In laboratory experiments under aerobic conditions, up to 50% of HA was utilized as a supplementary source of nutrients by an assemblage of soil microorganisms in only 21 days. The microbial utilization was enhanced to over 80%, and up to 98%, respectively, if HA served as the sole source of carbon or nitrogen. Remaining HA which could be re-isolated from microbial cultures were lower in carbon (<12%) and nitrogen (<2.3%). Spectroscopic analysis (UV, Vis, FTIR) indicated losses, especially in aliphatic structural units, and a relative enhancement in aromatic structures. It was postulated that for their high degree of degradability, HA indigenous to that anthropogenic environment would not play an important role in the long-term stabilization of landfill refuse.

Journal Article↗

In vitro anti-influenza virus activity of synthetic humate analogues derived from protocatechuic acid.

Two humic-like substances, the oxidative polymer of protocatechuic acid (OP-PCA) and humic acid inhibit the in vitro replication of influenza virus A/WSN/33 (H1N1) in Madin-Darby canine kidney (MDCK) cells at concentrations of no cytotoxicity. The 50% inhibitory concentration (IC50) for OP-PCA was 6.59 +/- 1.02 microg/ml when the compound was added at the stage of viral adsorption. When OP-PCA was added after virus adsorption, the IC50 was 53.27 +/- 8.12 microg/ml. The IC50 for humic acid was 48.61 +/- 7.32 microg/ml and 55.27 +/- 5.46 microg/ml respectively when the compound was added at the stage of viral adsorption or post-adsorption. In spite of structural resemblance of these two compounds, they exhibit different actions of anti-flu. The OP-PCA inhibits virus-induced hemagglutination and low pH-induced cell-cell fusion. Humic acid inhibits the endonuclease activity of viral RNA polymerase. The monomer of PCA shows no inhibition on influenza virus replication.

Animals↗

The effect of humic acids on the water solubility and water-organic carbon partitioning of fluorene and its NSO-heteroanalogues: carbazole, dibenzofuran, and dibenzothiophene.

The solubilizing effect of humic acids on fluorene and its NSO analogues carbazole, dibenzofuran and dibenzothiophene has been studied. The interaction between these substances and humic acids was found to depend significantly on the actual humic acid concentration. A pronounced decrease in the interaction constant, as well as in the water-organic matter partitioning coefficient was observed with increasing humic acid concentration. The effects are discussed in terms of concentration dependent macromolecular structural changes in the humic acids. A linear free energy relation for the interaction is suggested.

Benzofurans↗

Characterization of natural organic matter (NOM) derived from sewage sludge compost. Part 1: chemical and spectroscopic properties.

In this study changes in the properties of natural organic matter (NOM) were studied during composting of sewage sludge in a laboratory experiment using the pile method. Typical physicochemical parameters were measured during 53 days of composting including humic fractions. The effects of humification on the molecular properties of humic acids (HA) were investigated by 13C CP/MAS NMR spectroscopy. On the basis of chemical analyses, 53 days of composting sewage sludge with structural material can be divided into three phases: (i) domination of rapid decomposition of non-humic, easily biodegradable organic matter (two to three weeks), (ii) domination of organic matter humification and formation of polycondensed, humic-like substances (the next two weeks), (iii) stabilization of transformed organic material and weak microbial activity. Spectroscopic characterization (13C NMR) of compost humic acids reveals changes in their structures during maturation. The changes are highly correlated with the processes taking place in bulk compost.

Humic Substances↗

Comparative study of methods for extraction and purification of environmental DNA from soil and sludge samples.

An important prerequisite for successful construction of a metagenome library is an efficient procedure for extracting DNA from environmental samples. We compared three indirect and four direct extraction methods, including a commercial kit, in terms of DNA yield, purity, and time requirement. A special focus was on methods that are appropriate for the extraction of environmental DNA (eDNA) from very limited sample sizes (0.1 g) to enable a highly parallel approach. Direct extraction procedures yielded on average 100-fold higher DNA amounts than indirect ones. A drawback of direct extraction was the small fragment size of approx 12 kb. The quality of the extracted DNA was evaluated by the ability of different restriction enzymes to digest the eDNA. Only the commercial kit and a direct extraction method using freeze-thaw cell lysis in combination with an in-gel patch electrophoresis with hydroxyapatite to remove humic acid substances yielded DNA, which was completely digested by all restriction enzymes. Moreover, only DNA extracted by these two procedures could be used as template for the amplification of fragments of several 16S rDNA, 18S rDNA groups under standard polymerase chain reaction conditions.

DNA, Ribosomal↗

Bio-degradation of olive mill wastewater sludge by its co-composting with agricultural wastes.

The use of maize straw (MS) or cotton waste (CW) as bulking agents in the composting of olive mill wastewater (OMW) sludge was compared by studying the organic matter (OM) mineralisation and humification processes during composting and the characteristics of the end products. Both composts were prepared in a pilot-plant using the Rutgers static-pile system. The use of CW instead of MS to compost OMW sludge extended both the thermophilic and bio-oxidative phases of the process, with higher degradation of polymers (mainly lignin and cellulose), a greater formation of nitrates, higher total nitrogen losses and a lower biological nitrogen fixation. The CW produced a compost with a more stabilised OM and more highly polymerised humic-like substances. In the pile with CW and OMW sludge, OM losses followed a first-order kinetic equation, due to OM degradation being greater at the beginning of the composting and remaining almost constant until the end of the process. However, in the pile with MS and OMW sludge this parameter followed a zero-order kinetic equation, since OM degraded throughout the process. The germination index indicated the reduction of phytotoxicity during composting.

Agriculture↗

Fate and stability of 14C-labeled 2,4,6-trinitrotoluene in contaminated soil following microbial bioremediation processes.

Biological treatment of 2,4,6-trinitrotoluene (TNT) in soil rarely results in complete mineralization of the parent compound. More often, the largest proportion of the TNT carbon is incorporated into the soil organic matrix. Therefore, we evaluated the stability of nonextractable residues from various bioremediation processes of 14C-TNT in soils. The extractable amounts of the residual radioactivity varied between 7 and 33% and thus the nonextractable amount between 93 and 67% (3-15% in fulvic acids, 26-46% in humic acids, and 27-44% in the humin fraction). The residue-containing soils were analyzed for the release of radioactivity after treatment by physical (freeze and thaw, grinding of soil, and steam extraction), chemical (acid rain and addition of metal complexing agent), and biological methods (addition of compost, white rot fungi, radical-generating enzymes, and germination of plants). Freeze and thaw treatment and grinding of the soil did not alter the partitioning of the label significantly. Steam extraction and acid rain extraction increased the water extractability to 11 to 29% and to 51.6% in the native TNT-contaminated soil. The addition of ethylenediamine-tetraacetate (EDTA) increased the extractability from 7 to 12%. After biological treatment, only slightly increased extractability (<10%) was observed. No increase of extractable TNT or known metabolites was observed with any of the treatments. Thus, under the treatment conditions applied in this study, the residues formed during microbial transformation of TNT may be biogenic residues with low mobilization potential and low hazardous impact.

Agaricales↗