Oxidative degradation of 2,4,6-tribromophenol by SBA-15 supported metal tetrakis(1-methylpyridinium-4-yl)porphyrins in the presence of humic substances.

Metal tetrakis(1-methylpyridinium-4-yl)porphyrins were immobilized on sulfonated SBA-15 (MTMPyP-SO3-pr-SBA-15, M = Fe, Mn, Zn) for oxidative degradation of 2,4,6-tribromophenol in the presence of humic substances. The influence of the central metal of metalloporphyrins, pH, and catalyst dosage on the 2,4,6-tribromophenol degradation was investigated. FeTMPyP-SO3-pr-SBA-15 and MnTMPyP-SO3-pr-SBA-15 showed the catalytic activities. The activity of MnTMPyP-SO3-pr-SBA-15 was more strongly inhibited by humic substances than that of FeTMPyP-SO3-pr-SBA-15. Kinetic study indicated that humic substances suppressed the generation of high valent metal-oxo species in MnTMPyP-SO3-pr-SBA-15 at slightly acid condition. There was a clear linear relationship between the content of phenolic-OH and aromatic-C in humic substances and the corresponding inhibition ability. The inhibition by humic substances is probably ascribed to the coordination of humic substances with the monopersulfate species of MnTMPyP-SO3-pr-SBA-15, which prevented the formation of the reactive Mn-oxo species.

Effect of humic acids on the toxicity of pollutants to Chlamydomonas reinhardtii: Investigation by a microscale algal growth inhibition test.

Dissolved humic substances (DHSs) are the major components of organic matter in the aquatic environment. DHSs are well known to considerably affect the speciation, solubility, and toxicity of a wide variety of pollutants in the aquatic environment. In this study, the effects of the toxicity of heavy metals and hydrophobic organic pollutants (HOPs) on Chlamydomonas reinhardtii in the presence of humic acid (HA) were examined by a microscale algal growth inhibition (µ-AGI) test based on spectrophotometric detection. To clarify the relationship between the chemical properties of HAs and the toxicity change of pollutants, eight HAs from different sources were prepared and used. HAs were responsible for mitigating the toxicity of Hg, Cu, pesticides (γ-HCH, 2,4-D, and DDT), and polycyclic aromatic hydrocarbons (PAHs) such as naphthalene (Nap), anthracene (Ant), and benzo[a]pyrene (BaP). In particular, an approximately 100-fold decrease in the toxicity of BaP was observed in the presence of 10 ppm HAs extracted from tropical peat. The results indicated that the carboxylic group content and the HA molecular weight are correlated to the changes in the heavy metal toxicity. For HOPs, the aromaticity and polarity of HAs are crucial for mitigating their toxicity. Furthermore, it was clearly shown that the lake water including a high concentration of DHSs collected from Central Kalimantan, Indonesia, reduced the toxicity of Hg and γ-HCH on Chlamydomonas reinhardtii. Graphical abstract.

Biodegradation and Structural Modification of Humic Acids in a Compost Induced by Fertilization with Steelmaking Slag under Coastal Seawater, as Detected by TMAH-py-GC/MS, EEM and HPSEC Analyses.

The compost's humic acid (HA) content decreased when it was fertilized in coastal seawater with steelmaking slag, as confirmed. This study clarified the cause for this change by a detailed analysis of the structural changes in HAs based on the TMAH-py-GC/MS, HPSEC, and 3D-EEM spectra. An increase in the levels of pyrolysates of tannic acid with a low polymerization degree was attributed to the biodegradation of a high polymerized aromatic structure. Moreover, analyses of 3D-EEM, supported by HPSEC, indicated that approximately 20 kDa of the fluorescent matter was generated at the protein-like peaks (Ex/Em = 220/340 and 275/350 nm) in HAs derived from a mixture of compost with steelmaking slag. It would be caused due to the formation of HAs from the bacterial by-product by a catalytic reaction of the steelmaking slag. From these findings reported herein, we conclude that bio-degradation was a major reason for the decreased HA content, and the formation of HA from a part of the degradation products. This would be a reason for the structural modification of HA under the seawater condition.

Mechanism of the Elution of Iron from a Slag-Compost Fertilizer for Restoring Seaweed Beds in Coastal Areas-Characteristic Changes of Steelmaking Slag and Humic Acids Derived from the Fertilizer during the Elution Process.

The characteristic changes in steelmaking slag and humic acids (HAs) derived from a slag-compost fertilizer and their relation to the elution of Fe were evaluated in tank tests in Mashike, Hokkaido and Tsushima, Nagasaki. Analyses of iron, nitrogen and phosphate in the eluate, changes in the chemical states on the surface of the steelmaking slag, and the macro-structural features of the isolated HAs were investigated during the test. Temporal changes in Fe concentrations in the tanks were consistent with data collected in previous studies. Analyses of the surface by 57Fe Mössbauer spectroscopy showed that the concentration of Fe2+ in the fertilizer decreased and the ratio of Fe3+ increased, indicating that Fe2+ was preferentially eluted from the slag surface. The yields of HAs were significantly decreased during the test when steelmaking slag was mixed with compost. Changes in the UV-vis absorptivities indicated that de-aromatization had occurred. These results indicate that microorganisms that were present under these experimental conditions became activated by the mixing of compost with steelmaking slag, and are closely related to the continuous elution of Fe. The residual Fe in the fertilizer after the tests was investigated by analyzing seawater and the levels of extractable Fe. The trends for extractable Fe concentrations were consistent with the results obtained by 57Fe Mössbauer spectroscopy and UV-vis spectra.

Roles of Microbial Activity and Anthraquinone-2,7-disulfonate as a Model of Humic Substances in Leaching of Iron from Hematite into Seawater.

Fertilization with a mixture of steelmaking slag and compost can affect the supply of dissolved iron used to restore seaweed beds, however, the mechanisms of iron elution from the fertilizer are not well understood. In the present study, the microorganism was isolated from Fe-fertilizer incubated in coastal seawater for 6 months, and was identified as Exiguobacterium oxidotolerans by 16S rDNA sequencing. The iron elutability of the bacteria was proved based on the increasing of dissolved iron by incubation with Fe2O3 (hematite) under a seawater-like condition. The value of ORP was changed by inoculated of the bacteria from ca. 0 to ca. -400 mV, which is anticipated concerning to reduction of Fe. The concentration of eluted iron was largely depended on those of organic acids produced by bacteria. From the results, it was proved that E. oxidotolerans is capable of Fe reductive eluting of iron from Fe2O3 into seawater. Anthraquinone-2,7-disulfonate (AQDS), which can play as an electron acceptor/donor between microbe and insoluble Fe2O3 particles, enhanced the effect of iron bio-leaching.

Changes in the Structural Features of Organic Matter Extracted from Compost by the Seawater during a 90-day Period under Anaerobic Conditions, and Its Effect on Oogenesis of Brown Macroalga.

Seawater-extractable organic matter (SWEOM) has a potential to serve as an Fe complexing agent in an Fe-fertilizer intended to restore and preserve macroalgal forests. To better understand the restoration technique, structural alterations in SWEOM that occurred during a 90-day period of incubation in seawater were determined. Up to 82% of the total eluted SWEOM occurred during the initial 30 days; a small amount of SWEOM then continued to elute during the next 60 days. Spectroscopic analyses showed that the high-molecular-weight SWEOM fraction (HMW) altered in aliphatic-rich materials, while the low-molecular-weight fraction (LMW) became significantly enriched in aromatic structures. The structural alterations in the HMW and LMW could be caused by the action of anaerobic microorganisms. In addition, approximately 30 and 60% of the gametophytes were converted to eggs in the presence of HMW and LMW with Fe, respectively.

Potential risk of coupling products between tetrahalobisphenol A and humic acid prepared via oxidation with a biomimetic catalyst.

Tetrahalobisphenol A (TXPBAs, X = Br or Cl), TBBPA and TCBPA, which are widely used as flame retardants, ultimately disposed of in landfills. In landfills, enzymatically oxidized TXBPAs can be covalently incorporated into humic acids (HAs) to form coupling products (HA-TXBPAs). In the present study, HA-TXBPAs were prepared by catalytic oxidation with iron(III)-phthalocyanine-tetrasulfate as a model of oxidative enzymes. The stability of HA-TXBPAs was evaluated by incubating them under physicochemical conditions of landfills (pH 9 and 50 °C). For HA-TBBPA, 18-26% of TBBPA was released from HA-TBBPA, due to the acid dissociation of the loosely bound TBBPA. However, no additional release was observed, even after 30 days, indicating that 74-82% of the TBBPA was incorporated into the HA. For HA-TCBPA, 3-4% of TCBPA and a major byproduct, 4-(2-hydroxyisopropyl)-2,6-dichlorophenol, was found to be loosely incorporated into HA. For both TBBPA and TCBPA, covalently bound organo-halogens were not released during the 30 days of incubation. Inhibition of the growth of Chlamydomonas reinhardtii was indicated when trace levels of TXBPAs (approximately 0.1 µM) were present. These results suggest that HA-TXBPAs contain not only covalently incorporated TXBPAs but also loosely bound TXBPAs and halophenols. The latter in HA-TXBPAs have the potential to leach from landfills and affect aquatic ecosystems.

Advantages and risks of using steel slag in preparing composts from raw organic waste.

It had been reported that iron and manganese oxides in steel slag enhanced the production of humic acid (HA) from low-molecular-weight compounds, such as phenolic acids, amino acids, and saccharides. In the present study, this function of steel slag was applied to the composting of raw organic wastes (ROWs). The degree of humification of HAs is an important factor in evaluating compost quality. Thus, HAs were extracted from the prepared composts and the humification parameters were determined, in terms of elemental compositions, acidic functional group contents, molecular weights, spectroscopic parameters from UV-vis absorption and 13C NMR spectra. The timing for adding steel slag affected the degree of humification of HAs in the composts. The weight average molecular weight of a HA when slag was added initially (29 kDa) was significantly higher than when slag was added after elevating the temperature of the compost pile (17-18 kDa). These results show that ROWs are decomposed to low-molecular-weight compounds after the pile temperature is elevated and the presence of slag enhances the polycondensation of these compounds to produce HAs with a higher degree of humification. Because the slag used in the present study contained several-tens ng g-1 to several µg g-1 of toxic elements (B, Cu, Cr, and Zn), leaching tests for these elements from the prepared composts were carried out. Levels for leaching boron from composts prepared by adding slag (0.2-0.4 mg L-1) were obviously higher than the corresponding levels without slag (0.05 mg L-1).

Effects of humic acids derived from lignite and cattle manure on antioxidant enzymatic activities of barley root.

To investigate the effects of humic acids (HAs) on the ability of plants to defend themselves against oxidative stress, barley was hydroponically cultured in the absence and presence of HAs, and the antioxidant enzymatic activities (catalase, superoxide dismutase, ascorbate and glutathione peroxidases) of root tissue were evaluated. Auxin-like structures in HAs, which were extracted from an oxidation product of lignite (LHA) and compost derived from cattle manure (CHA), were identified by pyrolysis-gas chromatography/mass spectrometry (GC/MS) with tetramethylammonium hydroxide. The LHA, which had the lower molecular weight, was more effective in promoting the growth of barley root than CHA. However, the amounts of auxin-like structures in the CHA were much higher than those for LHA. The antioxidant enzymatic activities were initially decreased in the presence of LHA and CHA at the first day after refreshing the culture solution, but were significantly increased on the second day. The CHA sample, which contained relatively high levels of phenolic acids that contained auxin-like structures, was effective in increasing four types of enzymatic activities, while the activities of catalase and ascorbate peroxidase were increased in the presence of LHA, which contains naphthalene derivatives. These results indicate that using HAs as a supplement can be effective in enhancing antioxidation enzymatic activities, while the appearance of the effects is retarded because of the decomposition and release of auxin-like compounds from HAs by organic acids from the plant roots.

Risks and benefits of compost-like materials prepared by the thermal treatment of raw scallop hepatopancreas for supplying cadmium and the growth of alfalfa (Medicago sativa L.).

Scallop hepatopancreas, fishery waste, contains relatively high levels of Cd and organic nitrogen compounds, the latter of which represent a fertilizer. In this study, raw scallop hepatopancreas tissue was thermally treated with sawdust and red loam in the presence of an iron catalyst to produce compost-like materials (CLMs). Two CLM samples were prepared by varying the content of raw scallop hepatopancreas tissue: 46 wt.% for CLM-1 and 18 wt.% for CLM-2. Mixtures of control soil (CTL) and CLMs (CLM content: 10 and 25 wt.%) were examined for the growth of alfalfa (Medicago sativa L.) to evaluate the risks and benefits of using this material for fertilization. The Cd content in shoots and roots of alfalfa, that were grown in the presence of CLMs, was significantly higher than those for the plants grown in the CTL, indicating that Cd had accumulated in the plants from CLMs. The accumulation of Cd in the alfalfa roots was quite high in the case of the 25% CLM-1 sample. However, alfalfa growth was significantly promoted in the presence of 10% CLM-1. This can be attributed to the higher levels of nitrogen and humic substances, which serve as fertilizer components. Although the fertilization effect in case of CLM-1showed a potential benefit, the accumulation of Cd in alfalfa was clearly increased in the presence of both CLMs. In conclusion, the use of CLMs produced from raw scallop hepatopancreas tissue can be considered to have a desirable benefit from standpoint of its use as fertilizer, but is accompanied by a risk of the accumulation of Cd in alfalfa plants.

The oxidation of tetrabromobisphenol A by potassium monopersulfate with an iron(III)-phthalocyanine-tetrasulfonic acid catalyst in the presence of humic acid.

Tetrabromobisphenol A (TBBPA), a type of brominated flame retardant that shows endocrine disruption effects, has been identified in leachates from landfills. Iron(III)-porphyrins that mimic the active site of peroxidases have been shown to be effective in oxidizing halogenated phenols, such as TBBPA. In the present study, TBBPA was subjected to oxidation with potassium monopersulfate (KHSO5) using an iron(III)-phthalocyanine-tetrasulfonic acid (FePcTS), structural analogue of iron(III)-porphyrin, in the presence of humic acid (HA), a major component in landfill leachates. When TBBPA was oxidized using the above system, the levels of degradation and debromination increased with increasing pH in the presence of HA. Because of landfill leachates are weakly alkaline (around pH 8), oxidation products derived from TBBPA were investigated at pH 8. Approximately 48% of the bromine in the degraded TBBPA was incorporated into HA, and hydroxy-tribromobisphenol A was determined to be the major brominated intermediate in the HA fraction. In the iron(III)-porphyrin catalytic systems, the brominated intermediate incorporated into HA is mainly TBBPA, and no hydroxy-substituted bromophenols are found. Thus, the catalytic power of FePcTS is higher than that of iron(III)-porphyrin catalysts.

Comparison of the oxidation products produced by tetrahalobisphenol A flame retardants as a result of potassium monopersulfate oxidation with an iron(III)-tetrakis(p-sulfonatophenyl)porphyrin in the presence of humic acid.

Tetrabromobisphenol A (TBBPA) and tetrachlorobisphenol A (TCBPA), commercially used halogenated flame retardants, can be found in leachates from landfills, because hydrophobic interactions with humic acids (HAs), major organic components in landfills, result in an increase in their solubility. The oxidation characteristics of TBBPA and TCBPA in the presence of HA were compared using a catalytic system comprised of a combination of iron(III)-tetrakis(p-sulfophenyl)porphyrin (FeTPPS) and KHSO5 that can mimic the enzymatic reactions that occur in landfills. The levels of degradation and dehalogenation of TBBPA and TCBPA at pH 4 were significantly lower than at pH 8, which is a typical pH value for landfill leachates. In the presence of HA at pH 8, 2-hydroxyisopropyl-2,6 -dihalophenols (2HIP-26DXPs) were detected as major by-products. These compounds are likely produced via the ß-carbon scission of the substrates, and their levels decreased with increasing reaction time. The levels of coupling compounds between 2,6-dihalopnenols and TBBPA or TCBPA increased with reaction time. The 27% of Br in the degraded TBBPA and 50% of Cl in the degraded TCBPA were incorporated into the HA as a result of catalytic oxidation via the FeTPPS/KHSO5 system. These results suggest that TCBPA is incorporated into HA more readily than TBBPA. The coupling compounds between HA and halogenated intermediates from TBBPA or TCBPA were assigned by pyrolysis-gas chromatography/mass spectrometry.

Potassium monopersulfate oxidation of 2,4,6-tribromophenol catalyzed by a SiO2-supported iron(III)-5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin.

Iron(III)-porphyrin complexes are generally regarded as green catalysts, since they mimic the catalytic center of cytochrome-P450 and widely used as green catalysts for degrading halogenated phenols in wastewater, such as landfill leachates. However, iron(III)-porphyrins are deactivated by self-oxidation in the presence of an oxygen donor, such as KHSO5. In the present study, to enhance the reusability of an iron(III)-porphyrin catalyst, iron(III)-5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin (FeTCPP) was immobilized on a functionalized silica gel. The oxidative degradation of 2,4,6-tribromophenol (TrBP), a widely used brominated flame retardant that is found in landfill leachates, was examined using the prepared catalyst. In addition, the influence of humic substances (HSs), major components of leachates, on the TrBP oxidation was investigated. Concerning the effect of pH, more than 90% of the TrBP was degraded in the pH range of 3-8 in the absence of HS, while the optimal pH for the reaction was in the range of pH 5-7 in the presence of HS. Although the oxidation of TrBP was inhibited in the presence of HSs, more than 90% of the TrBP was degraded in the presence of 50 mg L(-1) of HS. Thus, the prepared catalyst, SiO2-FeTCPP, showed a high catalytic activity and could be reused up to 10 times even in the presence of HS.

Mitigation of peroxidative stress for barley exposed to cadmium in the presence of water-extractable organic matter from compost-like materials.

The effects of water-extractable organic matter (WEOM) from compost-like materials on peroxidative stress were investigated for hydroponic culture of barley exposed to Cd. In the presence of WEOM, lipoxygenase activity and malondialdehyde, indices of peroxidative stress in barley, were significantly reduced, compared to those with Cd alone (5 µM) for a 30-d culture (p<0.05). In addition, Cd uptake in the presence of WEOM samples was significantly lower than that in their absence (p<0.05). These results indicate that the addition of WEOM can be effective in mitigating the peroxidative stress in barley exposed to Cd. Of the total Cd in the solution, 7-8% was complexed with WEOM, indicating that the complexation of Cd with WEOM is a minor factor in reducing Cd-induced stress in barley. The WEOM sample was purified by cation-exchange column and ultrafiltration to remove the nutrient minerals, such as Ca, Mg and Fe. When the purified WEOM was employed for hydroponic culture in the presence of Cd, significant decreases in peroxidative stress and Cd uptake were observed (p<0.05). These results show that the organic components in WEOM contribute to the mitigation of peroxidative stress in barley exposed to Cd.

Determination of labile Fe(II) species complexed with seawater extractable organic matter under seawater conditions based on the kinetics of ligand-exchange reactions with ferrozine.

A fertilizer, comprised of a mixture of steel slag and compost, was used to restore seaweed beds in barren coastal areas. Complex Fe(II) species, supplied by steel slag, play a significant role in supplying Fe(II) to coastal areas and stimulating seaweed growth. Seawater extractable organic matter (SWEOM) from compost is generally assumed to serve as a chelator of Fe(II) in the fertilizer. It is considered that the bioavailability of Fe(II)-SWEOM complexes is higher in the dissociable (labile) species. In the present study, a method for determining labile species of Fe(II)-SWEOM complexes in seawater (pH 8.0, I = 0.7) was developed. The method is based on a ligand-exchange reaction between SWEOM and ferrozine (FZ). Because Fe(II) is readily oxidized to Fe(III) under normal seawater conditions, ascorbic acid was added as an antioxidant. The coloring for the Fe-FZ complex in the presence of SWEOM was retarded. This retarding can be attributed to a ligand-exchange reaction between FZ and labile Fe(II)-SWEOM complexes. Conditional binding constants for the labile Fe(II)-SWEOM complexes and binding capacities of labile sites in SWEOM to Fe(II) were evaluated for a variety of total Fe(II) concentrations.

Oxidative debromination and degradation of tetrabromo-bisphenol A by a functionalized silica-supported iron(III)-tetrakis(p-sulfonatophenyl)porphyrin catalyst.

Tetrabromobisphenol A (TBBPA), a commonly used brominated flame retardant, also functions as an endocrine disruptor. Thus, the degradation of TBBPA has attracted considerable interest among the scientific community. Iron(III)-porphyrin complexes are generally regarded as "green" catalysts and have been reported to catalyze the efficient degradation and dehalogenation of halogenated phenols in environmental wastewaters. However, they are quickly deactivated due to self-degradation in the presence of an oxygen donor, such as KHSO5. In the present study, an iron(III)-tetrakis (p-sulfonatophenyl)-porphyrin (FeTPPS) was immobilized on imidazole-modified silica (FeTPPS/IPS) via coordination of the Fe(III) with the nitrogen atom in imidazole to suppress self-degradation and thus enhance the catalyst reusability. The oxidative degradation and debromination of TBBPA and the influence of humic acid (HA), a major component in leachates, on the oxidation of TBBPA was investigated. More than 95% of the TBBPA was degraded in the pH range from 3 to 8 in the absence of HA, while the optimal pH for the reaction was at pH 8 in the presence of HA. Although the rate of degradation was decreased in the presence of HA, over 95% of the TBBPA was degraded within 12 h in the presence of 28 mg-C L⁻¹ of HA. At pH 8, the FeTPPS/IPS catalyst could be reused up to 10 times without any detectable loss of activity for TBBPA for degradation and debromination, even in the presence of HA.

Electrochemical genotoxicity assay based on a SOS/umu test using hydrodynamic voltammetry in a droplet.

The SOS/umu genotoxicity assay evaluates the primary DNA damage caused by chemicals from the ß-galactosidase activity of S. typhimurium. One of the weaknesses of the common umu test system based on spectrophotometric detection is that it is unable to measure samples containing a high concentration of colored dissolved organic matters, sediment, and suspended solids. However, umu tests with electrochemical detection techniques prove to be a better strategy because it causes less interference, enables the analysis of turbid samples and allows detection even in small volumes without loss of sensitivity. Based on this understanding, we aim to develop a new umu test system with hydrodynamic chronoamperometry using a rotating disk electrode (RDE) in a microliter droplet. PAPG when used as a substrate is not electroactive at the potential at which PAP is oxidized to p-quinone imine (PQI), so the current response of chronoamperometry resulting from the oxidation of PAP to PQI is directly proportional to the enzymatic activity of S. typhimurium. This was achieved by performing genotoxicity tests for 2-(2-furyl)-3-(5-nitro-2-furyl)-acrylamide (AF-2) and 2-aminoanthracene (2-AA) as model genotoxic compounds. The results obtained in this study indicated that the signal detection in the genotoxicity assay based on hydrodynamic voltammetry was less influenced by the presence of colored components and sediment particles in the samples when compared to the usual colorimetric signal detection. The influence caused by the presence of humic acids (HAs) and artificial sediment on the genotoxic property of selected model compounds such as 4-nitroquinoline-N-oxide (4-NQO), 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX), 1,8-dinitropyrene (1,8-DNP) and 1-nitropyrene (1-NP) were also investigated. The results showed that the genotoxicity of 1-NP and MX changed in the presence of 10 mg∙L-1 HAs. The genotoxicity of tested chemicals with a high hydrophobicity such as 1,8-DNP and 1-NP were decreased substantially with the presence of 1 g∙L-1 sediment. This was not observed in the case of genotoxins with a low log K(ow) value.

Binding characteristics and dissociation kinetics for iron(II) complexes with seawater extractable organic matter and humic substances in a compost.

A steel-slag/compost fertilizer can be useful in supplying complex Fe(II) species to barren coastal regions. Seawater extractable organic matter (SWEOM) was examined for use as a novel chelator of Fe(II) in the compost. The dissociation kinetics for Fe(II)-SWEOM were evaluated, based on the rate of ligand-exchange with ortho-phenanthroline. The ΔH(‡) for the Fe(II)-SWEOM (19 kJ mol(-1)) was significantly smaller than the corresponding values for Fe(II) complexes with humic substances (27 kJ mol(-1)), suggesting that the Fe(II)-SWEOM is kinetically less stable.

Enhanced humification by carbonated basic oxygen furnace steel slag--II. Process characterization and the role of inorganic components in the formation of humic-like substances.

Enhanced humification by abiotic catalysts is a potentially promising supplementary composting method for stabilizing organic carbon from biowastes. In this study, the role of steel slag in the transformation of humic precursors was directly characterized by measuring the variance in dissolved organic carbon (DOC), spectroscopic parameters (E(600)), and the concentration and molecular weight change of humic-like substances (HLS) during the process. In addition, a mechanistic study of the process was explored. The results directly showed that steel slag greatly accelerated the formation of HLS. The findings indicate that Fe(III)-and Mn(IV)-oxides in steel slag act as oxidants and substantially enhance the polycondensation of humic precursors. Moreover, the reaction appears to suppress the release of metals from steel slag to a certain extent under acidic conditions. This can be attributed to the cover of HLS on the external surface of steel slag, which is significant for its environmentally sound reuse.

Enhanced humification by carbonated basic oxygen furnace steel slag--I. Characterization of humic-like acids produced from humic precursors.

Carbonated basic oxygen furnace steel slag (hereinafter referred to as "steel slag") is generated during iron and steel manufacturing and is often classified as waste. The effect of steel slag on humification process was investigated. Catechol, glycine and glucose were used as model humic precursors from degraded biowastes. To verify that humification occurred in the system, humic-like acids (HLAs) were isolated and characterized structurally by elemental analysis, FTIR spectra, solid-state CP-MAS (13)C NMR spectra, and TMAH-Py-GC/MS. Characteristics of the steel slag-HLA were compared with those of HLAs formed in the presence of zeolite and birnessite, and with that of mature compost humic acid. The results showed that steel slag-HLA, like zeolite- and birnessite-HLA, is complex organic material containing prominent aromatic structures. Steel slag substantially accelerated the humification process, which would be highly significant for accelerating the stabilization of biowastes during composting (e.g. municipal solid waste, sewage sludge, and food waste).