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Humic substances affect the activity of chlorophyllase.

Three humic substances--humic acid, fulvic acid, and humin--were isolated from soils located in the northern and southern forests of the Yuanyang Lake Nature Preserve in northern Taiwan's Ilan County. Aqueous extracts of fresh wet soil and of three humic substances, at concentrations of 0.125, 0.25, and 0.5 mg/ml, were investigated for their effects on the activities of chlorophyllase a and b. Aqueous extracts of forest soils at the northern and southern bank, dominated by the pure vegetation of Formosan False cypress (Chamcaecyparis formosensis Matsum), stimulate both chlorophyllase a and b activities, while those of the southern bank, dominated by a Taiwanese Miscanthus (Miscanthus transmorrisonensis Hayata), inhibits such activities. All three humic substances, despite their soil sources, stimulate the activities of both chlorophyllase a and b. Fulvic acid stimulates more chlorophyllase a activity than either humic acid or humin. Humic acid stimulates more activity of chlorophyllase b than either fulvic acid or humin. Humin exhibited the least effect on chlorophyllase a and b. It is suggested that humic substances in the soil may accelerate the chlorophyll degradation of litter in the ecosystem and that chlorophyllase a and b may be different enzymes.

Benzopyrans↗

[Possibilities for purification of refuse seepage water by sand containing humic substances].

Sands containing humic substances are proposed for protection of ground water from refuse tip seepage waters which containing heavy metals and organic polluting agents. Such sands are produced and spoiled southern of Leipzig during uncovering of brown coal. Humic acids have qualities such as ion-exchange materials, form hydrogen bondes and are able to form salts and complexes. Besides they can adsorb and include other substances. This properties qualify the humic acids in contact with the grained structure of the sand to interactions with heavy metal ions and organic pollution agents in water such as oils, phenols, surface-active agents and organic phosphorus compounds. The installation of sands containing humic substances on the base of the refuse tip gives chances to prevent the migration of heavy metal ions and organic pollution agents in seepage waters on principle. On the other hand it is possible to use sands containing humic substances for cleaning of seepage waters and recovering of anorganic and organic useful materials. First practical tests with an refuse tip seepage water from the district Erfurt confirm the cleaning effect and the recovering of heavy metals.

Humans↗

Interaction of humic substances and hematite: FTIR study.

The present work extended the knowledge on the binding and complexation of humic substances( humic acid or fulvic acid) and hematite by Fourier transform infrared spectroscopy( FTIR) . The FTIR data gained gave the consist evidences by two different sampling preparation methods that the interaction mechanism between humic substances and hematite was mainly conform to the ligand-exchange involving carboxylic functional groups of humic substances and the surfaces sites of hematite. The present method, although associated with some uncertainties, provided an opportunity to increase the knowledge in this field.

Benzopyrans↗

Direct and interacting toxicological effects on the waterflea (Daphnia magna) by natural organic matter, synthetic humic substances and cypermethrin.

Humic substances are the main component of dissolved organic matter in all aquatic ecosystems, comprising a variety of molecular structures and functional groups. They bind organic pollutants and metals, thereby decreasing the bioavailability and consequently the toxicity of these substances in most instances. Recent studies also describe direct interactions and effects on organisms. Current studies also show that in some cases mitigation effects are stronger at lower concentrations of natural organic matter (NOM) and that toxicity increases with increased NOM concentrations. We hypothetise that at higher concentrations the mitigating effects are overlayed by direct effects of NOM themselves, thus these aspects were investigated in combination. So, on the one hand, this study demonstrates direct effects on toxicological parameters and activities of transformation enzyme systems of Daphnia magna, provoked by two NOM and one synthetic humic-like substance, HS1500. On the other hand, capacities of NOM and synthetic HS1500 to mitigate effects of the insecticide cypermethrin were investigated. Taken together, mitigation effects were overlayed by direct own effects of the NOM and HS1500. The NOM used were isolates from Suwannee River (XAD, Spring 2000) and from streams of the Svartberget forest (reverse osmosis, Spring 2000). The HS1500 was synthetically produced by radicalic autoxidation of hydroquinones. Suwannee River NOM at concentrations between 50 and 100 mg/l, and HS1500 (10-50 mg/l), but not Svartberget NOM increased immobility and lethality of the daphnids. All elevated the activity of the soluble glutathione S-transferase from 0.5 mg/l (HS1500), 1.0 mg/l (Suwannee River NOM) and 10 mg/l (Svartberget NOM) onwards, the microsomal glutathione S-transferase did not react. The glutathione peroxidase tended to increase. In the single exposure, the insecticide cypermethrin increased all toxicological parameters, elevated soluble and tendentially microsomal glutathione S-transferase activity between 0.001 and 1.0 microg/l and tendentially increased glutathione peroxidase. In contrast to that, 50 mg/l of the NOM and HS1500 did not mitigate toxicological effects. HS1500 in combination with cypermethrin even increased immobility, compared to cypermethrin alone. Increase of the NOM or HS1500 concentrations in combination with cypermethrin did not increase mitigation as seen in the activity of soluble glutathione S-transferases, activities of microsomal glutathione S-transferase and glutathione peroxidase even decreased, relative to control, which can be a hint of enzyme disfunction or further damages in the cell. An increase of concentration did not increase mitigation. Mitigation was higher at lower NOM or HS1500 concentration, probably as a consequence of the direct effects caused by themselves. Consequently, direct effects are relevant for analysing the mitigation qualities.

Animals↗

Mutagenicity from ozonation of humic substances.

Eight structural components of humic substances were ozonated. Mutagenic activity was found using TA100 with and without S9 mix for all ozonated components. p-Hydroxybenzaldehyde was chosen as an important component and ozonation products were determined by gas chromatography-mass spectrometry (GC-MS). Aldehydes, ketones and carboxylic acids were identified as the ozonation products. Among these products, acetaldehyde, formaldehyde, glyoxal, methylglyoxal and glyoxylic acid were recognized to be mutagenic. Furthermore, p-hydroxybenzaldehyde was first ozonated and then chlorinated. A great variety of chlorinated organic compounds, many of which are known mutagens, have been identified by GC-MS in the ether extract. The same compounds have previously been reported as chlorination products of humic substances. Aldehydic products by ozonation were identified from ozonation followed by chlorination of humic substances and p-hydroxybenzaldehyde.

Animals↗

Metal-modified silica adsorbents for removal of humic substances in water.

As novel adsorbents for humic substances, Fe-, Mg-, and Ca-modified silica gels SiO(2)Fe, SiO(2)Mg, and SiO(2)Ca were prepared, and their adsorbabilities to humic and fulvic acids were evaluated in water at 25 degrees C for 20 h. Among these adsorbents, SiO(2)Fe indicated the highest adsorbability, in which removing humic substances in water was accomplished to 80-97%. By calcination at 600 degrees C and washing with water, adsorbabilities of the silica adsorbents deteriorated except for the case of calcination of SiO(2)Ca. This is due to changing metal modification structures and losing chlorine, judging from elemental analysis, TG-DTA, and XPS. Especially, the modifier Fe was tightly fixed on the silica surface of SiO(2)Fe, since the metal content was almost constant even after the calcination and water washing unlike the other adsorbents. Therefore, we found that SiO(2)Fe is the most useful adsorbent among the silica adsorbents and that its modification structure is composed of SiOFe, FeCl, and FeOH. In addition, the adsorption mechanism is explained by an interaction between Fe and humic substance molecule having carboxylate and phenolate groups, accompanied with anion exchange of chloride ion Cl(-) for the humic substance molecule via the silica pores. SiO(2)Fe may be applied to an adsorbent alternative for charcoal in water purification plants, and the used SiO(2)Fe may be further reused as a fertilizer since humic substances have plant-glowing ability and silica strengthens plant parts.

Adsorption↗

The effects of polymer characteristics on nano particle separation in humic substances removal by cationic polymer coagulation.

Removal of humic substances by coagulation involves nano- and microparticle transport processes. The objective of this paper has been to describe the effects of polymer characteristics on the initial coagulation of nano-sized humic substances and on the aggregates' ability to form larger flocs. The study offers a direct comparison of four different low molecular weight polycations, with charge densities ranging from 4.0 to 7.0 meq/g, as well as of a low and medium molecular weight cationic polyacrylamide with practically equal charge densities. The extent of coagulation of humic substances, determined as the percentage removal of humic substances after filtration through 0.1 microm, could, regardless of the polymer type, be explained by the amount of cationic charge equivalents added per mg TOC of humic substances. The optimal polymer dosage with respect to the extent of flocculation, determined as the percentage removal after filtration through 11 microm could not be explained by this, but the maximum extent of flocculation obtained with each polymer type increased with increasing polyelectrolyte charge density. However, the weak polycation chitosan showed a significantly higher maximum extent of flocculation than would be predicted from its charge density. Polyelectrolyte molecular weight did not show any significant effect on the coagulation of humic substances, nor did it increase the extent of floc separability at 11 microm.

Cations↗

Vertical distribution and characteristics of soil humic substances affecting radionuclide distribution.

The humic substances extracted from different soil depths are separated into humic (HA) and fulvic (FA) acids, and characterized for their chemical composition, proton exchange capacity, spectroscopic characteristics and binding properties to the europium ion. The chemical and spectroscopic results show that FA compared to HA has a relatively high O/C ratio, high acidic functional group contents and low aromatic contents. The synchronous fluorescence spectroscopic results show that the stability constant (K) of the soil humic substances with Eu(III) ion tends to increase as the soil depth becomes deeper, and HA has a slightly stronger binding ability than FA. The measured total site concentrations (C(L)) reveal that Eu(III) ion is loaded onto HA by 62-77% of the total acid sites, but FA is only approximately 50% covered by Eu(III) ion. Information could be useful in understanding the migration of radionuclides in soil layer.

Benzopyrans↗

Hormonelike effects of humic substances on fish, amphibians, and invertebrates.

Humic substances comprise the majority of organic matter in freshwater ecosystems and were thought to be inert or refractory, except for photolytic degradation. However, evidence is increasing that humic substances interact with aquatic organisms similarly to weak anthropogenic chemicals with nonspecific and specific effects. One specific effect is a hormonelike effect, namely, modulation of the number of offspring, which was first described with the nematode Caenorhabditis elegans. Yet a hormonelike effect is not restricted to only the nematode. With the ornamental swordtail fish, Xiphophorus helleri, and the South African clawed frog, Xenopus laevis, we present phenomenological evidence that slight feminization occurred when these vertebrate species were exposed to a synthetic humic substance, a condensation product of polyphenols. The slight feminization was dose dependent.

Animals↗

Characterization of humic substances isolated from Han River water and change in the structural and chemical characteristics by ozonation.

This study investigated the characteristics of extracted humic substances, which are ubiquitous in river waters and affect the treatment of water. Humic substances were extracted from the Han River water and analyzed using the samples obtained before/after ozonation with various analytical items. Ozonation was conducted in a batch-type reactor, and ozone was dosed from 0 to 2.0 mg O3 mg(-1) humic substances. The humic fraction was 56.0% of total organic carbon in the Han River and the ratio of fulvic to humic acids was approximately 3.46, including aromatic ring structures and/or various functional groups. Humic substances could not completely be oxidized to CO2, H2O, etc., but partly oxidized to low molecular weight matter, thus low removal efficiencies in terms of dissolved organic carbon (31% at 1.0 mg O3 mg(-1) humic substances) were observed. For UV absorbance at the wavelength 254 nm, ozone dose at 1.0 mg O3 mg(-1) humic substances showed more than 80% removal efficiencies. The molar ratios of H/C and O/C of the humic substances structure relatively increased by ozonation, indicating the degradation of aromatic groups in the humic substances molecule. The Fourier transform infrared spectra and proton nuclear magnetic resonance spectra of humic substances showed the increase in carboxylic acids and the decrease in aromatic protons through ozonation, respectively. As specific reaction sites in the humic substances including aromatic ring structures were reduced through ozone oxidation, contents of carboxylic acids, ketones and quinones in the humic substances molecule increased.

Bioreactors↗

Sono-oxidation treatment of humic substances in drinking water.

Currently humic substances are removed from the raw water prior to chlorination by the conventional coagulation and filtration method using aluminium sulphate. Application of high-intensity (> 10 W/cm2) ultrasonic irradiation in conjunction with oxidative process using commercial oxidants H2O2 was investigated as an alternative. Sono-oxidation and sonodegradation of natural and synthetic humic substances have been followed over time by measuring total organic carbon (TOC) and absorbance by ultraviolet spectrometer (UV-VIS). It took approximately 60 min to reduce TOC by half and to have a complete degradation of humic acid.

Carbon↗

The interaction of humic substances with cationic polyelectrolytes.

The anionic charge carried by aquatic humic substances plays a major part in their interaction with metal ions and other cationic species. Removal of such substances by coagulation and flocculation can be, at least partly, determined by charge neutralisation. In this work, the charge densities of a commercial humic acid and an aquatic humic extract have been investigated by studying their interactions with a series of synthetic cationic polyelectrolytes. These covered a range of charge densities and molecular weights. The techniques used were colloid titration by spectrophotometry and streaming current detection, and flocculation determined by colour removal and by an optical monitoring method. For a given cationic polyelectrolyte, all four methods gave charge densities for humic substances which were in good agreement. However, systematic differences in the apparent humic charge density were found, depending on the charge density of the cationic polyelectrolyte used. With low charge density polyelectrolytes, the apparent anionic charge of the humic substances was found to be low. With higher polyelectrolyte charge densities, the apparent humic substance charge density increases and reaches a limiting value when the polyelectrolyte charge is greater than about 3 meq/g. This indicates a non-stoichiometric interaction between the anionic sites of the humic substances and the cationic charges of the low-charge polyelectrolytes. Optimum flocculation of humics occurred with less cationic charge in the case of low-charge polyelectrolytes than those with higher charge density. However, the degree of removal was considerably better in the latter case. In all cases, the molecular weight of the cationic polyelectrolytes (over a range from about 50,000 to 15 million) appeared to have no effect on the results.

Cations↗

Iodine in drinking water in Denmark is bound in humic substances.

OBJECTIVE: The iodine intake level is important for the occurrence of thyroid disorders in a population. We have previously found that iodine in drinking water is related to iodine excretion but whether iodine is present as iodide or bound in other molecules remains unknown. DESIGN: We measured iodine in drinking water from 22 locations in Denmark. Six locations were selected by iodine content for further tap water analysis (Skagen 140 micro g/l, Samsoe 56 micro g/l, Nykoebing S. 50 micro g/l, Nakskov 40 micro g/l, Ringsted 38 micro g/l, Copenhagen 19 micro g/l). METHODS: HPLC size exclusion before (Skagen) and after (all sites) freeze drying and measurement of absorbance (280 nm) and iodine in fractions, and fluorescence spectroscopy of bulk organic matter in Skagen drinking water. RESULTS: Iodine content was unaltered after 3 Years (P=0.2). All samples contained organic molecules with characteristics similar to humic substances. Most iodine eluted with humic substances (Skagen 99%, Ringsted 98%, Nykoebing S. 90%, Copenhagen 90%, Samsoe 75%, Nakskov 40%). Changing pH and ionic strength and preincubation with iodide indicated that iodine was bound in humic substances. Humic substances may affect thyroid function but differ with geology. Geological and geochemical data agree with tap water humic substances having been released from marine deposits. Iodine is abundant in the marine environment and marine deposits are particularly rich in iodine. Correlation analysis (r=0.85, P=0.03) conform to iodine in drinking water, suggesting marine humic substances at the source rock. CONCLUSION: Iodine in Danish drinking water varied considerably. In drinking water with a high iodine content, the iodine mainly eluted with humic substances derived from marine source rock. We hypothesize that iodine in drinking water in general suggests coexisting humic substances of marine origin.

Denmark↗

Generation of mutagenicity by ozonation of humic substances' components.

Components of humic substances, such as vanillin, syringaldehyde, vanillic acid and di-n-butylphtalate, were ozonated and subjected to the mutagenicity assay using Salmonella typhimurium TA 98 and 100 with and without S9 mix. The strong mutagenic activity was found on all components except di-n-butylphtalate by strain TA 100 with and without S9 mix. Substances with strong mutagenic activity in ozonated vanillin were water-soluble and were slightly extracted with benzene, dichloromethane and ethyl acetate. Following gel chromatography on Sephadex G-10, the strong mutagens generated by ozonation were found with molecular weights greater than 300.

Animals↗

The relationship between disinfection by-product formation and structural characteristics of humic substances in chloramination.

The influence of structural characteristics of humic substances on disinfection by-product (DBP) formation was investigated for seven humic substances isolated from aquatic and terrestrial sources. The structural characterizations included 13C nuclear magnetic resonance (13C NMR) spectroscopy and ultraviolet (UV) spectroscopy. The aqueous humic substances were chloraminated at pH 7.0 and 8.5, with and without the presence of the bromide ion, and analyzed for total organic halogen (TOX), trihalomethanes (THMs), and haloacetic acids (HAAs). Aromatic contents determined by 13C NMR and differential UV absorbance at 254 nm statistically correlated with TOX formation for the humic substances investigated at p < 0.08. In contrast, a lack of correlation was observed for THM and HAA formation and these parameters. This paper also compiles relevant literature and discusses the contrasting reaction response of DBP precursor material to chlorination and chloramination.

Chloramines↗