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Effects of cyclodextrins on photodegradation of organophosphorus pesticides in humic water.

Cyclodextrin (CyD) effects on photodegradations of organophosphorus pesticides in humic water were monitored on the basis of the increase percentage of the photodegradation rate constant for CyD-containing humic water. Remarkable promotion effects of CyDs were observed in humic water for photo-induced radical generation. The promotion effects could be mainly assigned to the inclusion effects of CyDs to catalyze interactions of pesticides with reactive radicals generated by the humin photosensitizer and inclusion-trapped in CyDs.

Cyclodextrins↗

Photodegradation of humic acids in the presence of hydrogen peroxide.

A batch photoreactor was used to evaluate the UV/H2O2 oxidation process for the removal of humic acids in water. A 450-W UV lamp with high-pressure mercury vapor was employed as the light source. The residues of humic acids and hydrogen peroxide were measured for assessment of process performance and understanding of process reaction behavior. The UV photolysis alone can play an important role in the degradation of humic acids. The presence of hydrogen peroxide was found to promote the degradation efficiency. However, excessive dosage of H2O2 does not further improve the degradation of humic acids. On the contrary, the lower the H2O2 dosage the higher the amount of humic acids which can be removed. Aeration with air does not favor the removal efficiency of humic acids as the oxidation lasts for a sufficiently long time. The presence of carbonate species deteriorates the humic acids' removal, whereas it results in a larger amount of H2O2 decomposition.

Chelating Agents↗

Photoinductive properties of soil humic acids and their fractions obtained by tandem size exclusion chromatography-polyacrylamide gel electrophoresis.

Humic acids (HAs) from three soils of different origin (Chernozem, Ferralsol and Ranker) have been fractionated by coupling size exclusion chromatography (SEC) and polyacrylamide gel electrophoresis (PAGE) on three fractions (fractions A, B, C + D) with different molecular sizes (MSs) and exactly defined electrophoretic mobility (EM). Fractions identically marked had similar EM and MS, independently of HA sources. The photoinductive properties of the whole HAs and their fractions were compared by studying the photoinduced transformation of fenuron at 365 nm. High MS fractions A and B appeared to exhibit poor photoinductive activities compared to the whole HAs, whereas low MS fraction C + D in Chernozem and Ranker were more efficient than the whole HAs. A fourth intermediary fraction containing a mixture of fractions B and C + D with small amount of D was shown to photoinduce poorly the transformation of fenuron. It was therefore concluded that the molecules capable of photoinducing the transformation of fenuron were mainly contained in fraction D. Fluorescence properties of Chernozem HA and its fractions have been tested. Fraction C + D exhibited a very similar fluorescence emission spectrum in comparison with the whole HA and in contrast, the fractions A and B emitted very weakly.

Chromatography↗

Removal of metal ions and humic acid from water by iron-coated filter media.

Iron oxide is an excellent, regenerable adsorbent, and often controls free metals through adsorption reaction. The utilization of heating process for coating iron oxide on sand surface allowed the media to be used in a packed column. Iron-coated sand was investigated for adsorbing metal ions and natural organic matter from water by batch and column experiments. Chemical analysis (energy dispersive analysis of X-ray, EDAX) was used for characterizing the copper and lead adsorption sites on iron-coated sand. From the batch experiment results, the copper and lead ions could be removed simultaneously by the iron-coated sand in the competition adsorption system. The interaction between copper, lead ions and iron oxide on sand surface was primarily the chemical bonds. The maximum adsorption capacities of iron-coated sand for copper and lead were 0.259 mg Cu/g-sand and 1.211 mg Pb/g-sand, respectively. The presence of humic acid led to increase the adsorption of copper and lead. Results from column experiments indicated that the copper ions, lead ions and humic acid could be removed completely before the breakpoint. Consequently, the iron-coated sand may be applied for the adsorption/filtration of metal ions and natural organic matters from water.

Adsorption↗

Effects of selected metal ions on photodegradation of organophosphorus pesticides sensitized by humic acids.

Selected metal ions having paramagnetic property were found to exert inhibition effects on aquatic photodegradation of organophosphorus pesticides sensitized by humic acids, according to the increasing order of Cr(III) < Co(II) < Mn(II) < Cu(II). Basic factors dominating the metal-ion effects were clarified on the basis of the fluorescence quenching as well as radical scavenging abilities of metal ions complexed with humic acids.

Humic Substances↗

Role of cupric ions in the H2O2/UV oxidation of humic acids.

The purpose of this study is to reveal the role of cupric ions as a natural water contaminant in the H2O2/UV oxidation of humic acids. Humic acids are naturally occurring organic matter and exhibit a strong tendency of complexation with some transition metal ions. Chlorination of humic acids causes potential health hazards due to formation of trihalomethane (THM). The removal of THM precursors has become an issue of public concern. The H2O2/UV process is capable of mineralizing humic acids due to formation of a strong oxidant, hydroxyl radicals, in reaction solution. Experiments were conducted in a re-circulated photoreactor. Different cupric concentrations (0-3.8 mg/l) and different pH values (4-9) were controlled to determine their effects on the degradation of humic acids, UV light absorbance at 254 nm, and H2O2. The presence of cupric ions inhibits humic mineralization and decreases the rate of destruction of humic acids which absorb UV light at 254 nm. On the other hand, the higher the cupric concentration, the lower the H2O2 decomposition rate. In the studied pH range, the minimum of total organic carbon (TOC) removal occurs at pH = 6 in the presence of 2.6 mg/l of cupric ions; both acidification (pH = 4) and alkaline condition (pH = 9) lead to a better removal of TOC. It is inferred from this study that the cupric-complexed form of humic acids is more refractory than the non-complexed one.

Copper↗

Humic complexes of diethyl phthalate: molecular modelling of the sorption process.

The sorption mechanisms and complex formation between humic acid (HA) and a successively increasing number of diethyl phthalate (DEP) molecules have been studied theoretically using molecular mechanics, the number (n) of DEP molecules being varied from 1 to 30. The energy components of the single HA x nDEP complexes have been used as explanatory variables in a principal component analysis for exploring the presence of similarities/dissimilarities in the energetic properties of the individual xenobiotic complexes. The sorption can be explained in terms of a two-step mechanism. Absorption takes place as long as the host humic acid structure offers (a) enough internal docking space and (b) favorable interactions (energy release) with the guest molecule. This takes place for up to 7 DEP molecules. Further increase in the number to 30 DEP molecules will, due to the lack of free available internal voids, lead to surface controlled adsorption. The two-step sorption process apparently results in (a) a linear increase in energy gain by DEP bonds, and similarly (b) a constant incremental rise in molecular properties of the complexes such as volume and surface area. Three outstanding observations emerge: (1) Structural features at the atomic level (nanochemistry), such as partial atomic charges and high aromaticity of the humic acid, are observed to be dominating the intermolecular interactions in the complexes at the specific sorption sites. (2) Torsional relief and favorable changes in bonding energy also prevail for the growing complex. The latter indicates both the structural flexibility of the HA host and the stabilizing effect of DEP on the complex, by filling of the voids within the HA molecule. (3) The intermolecular forces are described mainly by hydrogen bonds (electrostatic energy) and interactions between dipole-dipole, such as carboxylic functions and uncharged moieties such as aromatic rings (van der Waals energy).

Absorption↗

Investigation of the permeability of humic molecules using zeta potential measurements.

Zeta potential measurements have been performed on colloidal humate in the presence of differing concentrations of sodium ions at pH = 6.0. A series of calculations has been performed in which the radius of the humic colloid was varied until the predicted surface potential was equal to the experimentally determined zeta potential. The results of the calculations showed that as the ionic strength increases, the apparent radius of the colloid decreases. Similar calculations in which a model colloid was treated as a rigid sphere, i.e., the radius of the colloid was kept constant, failed to simulate the observed zeta potential measurements.

Colloids↗

Photodegradation of ethylenediaminetetraacetic acid (EDTA) and ethylenediamine disuccinic acid (EDDS) within natural UV radiation range.

The rate of photodegradation of two chelating agents, ethylenediaminetetraacetic acid (EDTA) and an isomeric mixture of ethylenediamine disuccinic acid (EDDS), was analysed in humic lake water and in distilled water using exposure to sunlight, and in the laboratory using lamps emitting UV radiation in the range 315-400 nm. Degradation was studied using Fe(III) complexes and sodium salts of chelates. Fe(III) complexes were illuminated at pH 3.1 and 6.5. The results demonstrated that the rate of photodegradation of Fe(III)-EDTA and Fe(III)-EDDS complexes seems to be pH dependent. In the laboratory experiments degradation occurred much faster when the original pH was 3.1 rather than 6.5. The photodegradation of the isomeric mixture of EDDS was markedly faster than the degradation of EDTA both in the laboratory and field experiments, and both in humic and distilled water. The results indicated that in natural waters photodegradation of EDDS is independent of initial speciation of EDDS, while degradation of EDTA is dependent on its existence as Fe(III)-EDTA species.

Edetic Acid↗

Molecular size distribution of natural organic matter in raw and drinking waters.

The purpose of this study was to compare the molecular size distribution (MSD) of natural organic matter (NOM) in raw waters (RW) and drinking waters (DW), and to find out the differences between MSD after different water treatment processes. The MSD of NOM of 34 RW and DW of Finnish waterworks were determined with high-performance size-exclusion chromatography (HPSEC). Six distinct fractions were generally separated from water samples with the TSK G3000SW column, using sodium acetate at pH 7 as an eluent. Large and intermediate humic fractions were the most dominant fractions in surface waters (lakes and rivers), while in artificially recharged groundwaters and natural groundwaters intermediate and small fractions predominated. Water treatment processes removed the two largest fractions almost completely shifting the MSD towards smaller molecular size in DW. Granular activated carbon (GAC) filtration, ozonation, and their combination reduced all humic fractions compared to the conventional treatment. Humic fractions correlated with total organic carbon (TOC) content and chemical oxygen demand, this being especially true in RW. The results demonstrate that the HPSEC method can be applied for a qualitative and also for rough estimate quantitative analyzes of NOM directly from RW and DW samples without sample pretreatment.

Carbon↗

Oxidation of chlorophenols in soil at natural pH by catalyzed hydrogen peroxide: the effect of soil organic matter.

This investigation reports on the effects of soil organic matter (SOM) during the oxidation of chlorophenols with Fe2+-catalyzed H2O2 (Fenton oxidation) system. The soil pH was 7.1 and was not altered. Sorption experiments of soil pre-treated under various oxidation conditions were performed. Concentrations of organic matter in the liquid phase and soil before and after oxidation were analyzed. The results were correlated to the observation in batch Fenton oxidation tests. They showed that the oxidation of chlorophenols at natural soil pH depended on the dose of H2O2 and Fe2+. The soil organic content did not vary significantly after various Fenton treatments, while the sorption of chlorophenols was 10-25% less by the oxidation. The concentration of chlorophenols in the liquid phase exhibited a "decrease and rebound" phenomenon in the batch Fenton oxidation tests. It appeared that the oxidation of SOM resulted in the release of sorbed chlorophenols which were then oxidized by the excess H2O2. An "oxidation-desorption-oxidation" scheme was proposed to describe one of the interaction mechanisms among the oxidant, SOM, and chlorophenols during oxidation.

Adsorption↗

Soil phosphorus fractions in solution: influence of fertiliser and manure, filtration and method of determination.

This study investigated the forms of soil P released to solution, accuracy of their determination, and influence of colloids on P sorption/desorption dynamics. A Hagerstown silt loam, amended with dairy and poultry manure or superphosphate at five rates (0, 25, 50, 100, and 200 kg P ha(-1)), was extracted at two soil:solution ratios (1:5 and 1:100) and filtered at three pore sizes (0.8, 0.45, and 0.22 microm). Results showed that relative to the proportion of dissolved organic P (DOP, determined as the difference between total dissolved P [TDP] and P detected by ion chromatography), DRP increased with amendment rate. Relative to Mehlich-3 extractable P, DRP exhibited a power relationship with a much greater potential for soil P release at concentrations in excess of ca. 50 mg Mehlich-3 P kg(-1). Concentrations of DRP, determined by the acid molybdate method, were on average 12.5% greater than P detected by ion chromatography indicating P was solubilised during colorimetric determination. A linear relationship was found between total Al and DRP, which could indicate acid mediated hydrolysis of A1-humic-P substances, although acid mediated desorption of P from colloids cannot be discounted. No difference in solubilised P was found between solutions filtered at 0.22 and 0.45 microm, but was found between 0.8 microm and smaller filter sizes. Organic P extracted from manured soils was more recalcitrant than that extracted from soils amended with superphosphate, the later attributed to its accumulation in more labile pools. The sorption/desorption of P by colloids in solution were greatly affected by the rate of amendment and the soil:solution extraction ratio. More P was sorbed by superphosphate solutions compared to dairy manure amended soil solutions and was attributed to the saturation of colloidal P sorption sites by organic matter. In order to minimise the effects of colloids on P dynamics and the potential for hydrolysis in solution, filtration to at least 0.45 microm is required. However, soils with a lesser aggregate stability may require additional filtration.

Absorption↗

Reducing the formation of disinfection by-products by pre-ozonation.

The objective of this study is to apply the pre-ozonation process to reduce the formation of disinfection by-products (DBPs). The raw water sample, collected from the Te-Chi Reservoir in central Taiwan, has been polluted by fertilizer. Three types of resins were used to isolate the natural organic matter into seven types of organic fractions. The pre-ozonation was used to oxidize each organic fraction to study the reduction of DBPs of each fraction. Experimental results indicated that the pre-ozonation could reduce the concentration of dissolved organic carbon resulting in the reduction of DBP formation. With the pre-ozonation, 9-54% of DOC and more than 40% of DBPs were reduced. With the analysis of UV adsorption and Fourier transform infrared spectrometer (FTIR), the reduction of A254 and unsaturated functional groups such as aromatic ring and C=C bond containing in the water sample is the major reaction mechanism.

Benzopyrans↗

Effect of dissolved humic matters on the leachability of PCDD/F from fly ash--laboratory experiment using Aldrich humic acid.

The effect of dissolved humic matters (DHM) on the leachability of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) in fly ash was studied theoretically and in laboratorial condition to verify the previous results for pilot and field experiment of incineration residues landfill. In theoretical review, it was shown that DHM could influence the actual solubility and leachability of PCDD/F. The higher concentration of DHM showed the higher leachability of PCDD/F. In the leaching test, three different DHM concentrations and pHs of solutions were adopted to fly ash samples imaging the various characteristics of municipal solid waste leachate. It was proved experimentally that the leachability of PCDD/F increased with increasing DHM concentration in all pH conditions. The highest leachability was shown at the highest pH. Isomer distribution patterns of PCDD/F in all leachates were similar in all pH conditions. It backed up the distribution theory of PCDD/F between DHM and water.

Benzofurans↗

The importance of the short-term leaching dynamics of wood preservatives.

The potential environmental impacts from the use of treated timber in aquatic areas is under scrutiny as a result of environmental legislation and reports of the deleterious environmental effects around treated structures. In this study leaching experiments of up to 3 weeks duration were conducted on two species of chromated copper arsenate treated timber, dried for different periods of time. Increased drying time significantly reduced leaching of Cr and As. The addition of a synthetic humic acid increased leaching of Cu and As, but reduced leaching of Cr. Putative risk assessments conducted using short-term copper leaching data suggested protocol design may influence decisions made regarding the environmental acceptability of such preservatives.

Arsenates↗

Spectroscopic characterization of the structural and functional properties of natural organic matter fractions.

Natural organic matter (NOM) is known to be complex in nature with varying structural and functional characteristics. In this study, an aquatic NOM was fractionated into the polyphenolic-rich (NOM-PP) and the carbohydrate-rich (NOM-CH) fractions in an attempt to better characterize their chemical and structural properties along with a reference soil humic acid (SHA). Various spectroscopic techniques were employed for the study, including ultraviolet-visible (UV/Vis). 13C-nuclear magnetic resonance, Fourier-transform infrared, fluorescence, and electron paramagnetic resonance spectroscopies. Results indicate that the relative abundance of aromatic C=C and methoxyl (-OCH3) functional groups are in the order of SHA > NOM-PP > NOM-CH. However, the aquatic NOM-PP and NOM-CH fractions are characterized by high contents of carboxylic and alcoholic functional groups relative to the SHA. In particular, the NOM-PP fraction appears to contain more phenolic and ketonic functional groups than the NOM-CH and SHA fractions, and it gives a strong fluorescence and high paramagnetic spin count. On the other hand, the NOM-CH fraction possesses a relatively low amount of carbon but a high amount of oxygen or oxygen-containing structural features, such as carbohydrate-OH and carboxylic groups, and shows the least fluorescence intensity and paramagnetic spin counts. Results of these spectroscopic studies confirm the heterogeneous nature of NOM, and point out the importance of isolation and improved characterization of various NOM subcomponents in order to better understand the behavior and roles of NOM in the natural environment.

Humic Substances↗

Comparison of hydrolysis/coagulation behavior of polymeric and monomeric iron coagulants in humic acid solution.

Fluorescence quenching is commonly used to study the extent of metal binding to humic acid or fulvic acid. By studying this phenomenon, the hydrolysis and precipitation behaviors of polymeric and monomeric iron coagulants in the coagulation of humic acid were evaluated. Combined measurements of fluorescence intensity and dissolved organic carbon were performed to distinguish the hydrolysis and organic matter binding of polymeric and monomeric iron salts in coagulating high molecular weight organic compounds. Experimental results showed that ferric chloride had lower fluorescence quenching than polyferric sulfate (PFS), indicating more rapid hydrolysis of the monomeric ferric ion in the coagulation and dilution process. The less fluorescence quenching was caused by the lower residual concentration of Fe-humic acid complexes in the filtrate. There was no clear difference in adsorption ability and fluorescence quenching, which indicated that the physical and chemical properties of Fe(OH)3 flocs formed from PFS and FeCl3 coagulation were similar. From the pH study, we found that sludge formed from PFS coagulation was more stable than that from FeCl3 coagulation.

Chemical Precipitation↗

Structural characterisation of humic acid-bound PAH residues in soil by 13C-CPMAS-NMR-spectroscopy: evidence of covalent bonds.

The fate of 13C-labelled phenanthrene and fluoranthene in different soil systems during biodegradation was studied. The soil humic acid fraction was isolated followed by structural characterisation using 13C-cross polarisation magic angle spinning nuclear magnetic resonance spectroscopy (13C-CPMAS-NMR). It could be demonstrated that especially the ratio between the concentrations of polycyclic aromatic hydrocarbons (PAHs) and soil humus matrix limits the usefulness of this analytical tool. Based on these results a ratio of 13C-activity(PAH)/13C-activity(soil) approximately 1.5/1.0 in the test material was suggested. The chemical transformation of a PAH and its bound residue formation in a soil system detected by changes of chemical shifts in the 13C-NMR spectrum was proven for the first time. Structural information obtained by NMR spectra were verified by alkaline hydrolysis of PAH/humus-associations and following identification of cleavage products. Ester-bound phenanthrene metabolites such as 1-hydroxy-2-naphthoic acid, ortho-phthalic acid and 3,4-dihydroxybenzoic acid were detected. Additional structural assignments indicated the presence of ether-bound phenanthrene derivatives as well. Using isotopic labelling techniques a quantitative evaluation of bound residue distribution was undertaken. Fifty to seventy percent of phenanthrene metabolites which could be related to the added 13C(1)-phenanthrene were ester bound via their carboxyl groups.

Biodegradation, Environmental↗