Photoinductive efficiency of soil extracted humic and fulvic acids

Humic and fulvic acids extracted from soils of different genesis were investigated for their ability to photoinduce the transformation of fenuron (2 x 10(-4) mol(-1)) at 365 nm. The ratio of the initial rate of fenuron consumption over the rate of light absorption by humic substances was found to be higher for fulvic acids (range 2.0 x 10(-3) to 9.0 x 10(-5)) than for humic acids (range 1.7 x 10(-4) to - 3.6 x 10(-5)). Within the FAs population, this ratio decreased as the specific absorption coefficient at 365 nm increased. It seems therefore that most of 365-nm absorbing components have no photoinductive activity and even reduce that of photoinductive chromophores.     

Biodeterioration of cardboard-based liquid containers collected for fibre reuse

Liquid packaging board (LPB) collected in Germany is processed in Finland as recycled fibre and as plastic reject for incineration. The chemical, biological and physical changes occurring in recycled LPB bales were monitored during storage of six and 18 months. The moisture content in the core of the bales ranged from 7% to 53%, and pH values varied from 6.0 to 8.5. The average amount of mesophilic bacteria per container was 1.5 x 10(7) - 5 x 10(8), which means that recycled LPB pulp cannot be recommended for sanitary use. The concentration of CO2 inside the bale is an indicator of the activity of aerobic microorganisms and might be suitable for identifying deteriorated bales and removing them from the production line. Insects were found in some bales and the more deteriorated the bale was the more species of insects were found. The results showed the conversion of cellulose into humic acids to be clearly underway in some recycled LPB bales. The bale samples were extracted into hot water and into fulvic acids and humic acid (HA) fractions. The concentration of the humic acid fraction varied in the range 0.3-0.6% of the organic matter in fresh bales and 2.2% in one old bale. During aging nitrogen was enriched in all fractions.     

Comparison of structural features of water-soluble organic matter from atmospheric aerosols with those of aquatic humic substances

Elemental analysis, Fourier transform infrared coupled to attenuated total reflectance (FTIR-ATR) and solid-state cross polarization with magic angle spinning-¹³C-nuclear magnetic resonance (CPMAS ¹³C NMR) spectroscopies were used to compare the chemical features of water-soluble organic compounds (WSOC) from atmospheric aerosols with those of aquatic humic and fulvic acids. The influence of different meteorological conditions on the structural composition of aerosol WSOC was also evaluated. Prior to the structural characterisation, the WSOC samples were separated into hydrophobic acids and hydrophilic acids fractions by using a XAD-8/XAD-4 isolation procedure. Results showed that WSOC hydrophobic acids are mostly aliphatic (40–62% of total NMR peak area), followed by oxygenated alkyls (15–21%) and carboxylic acid (5.4–13.4%) functional groups. Moreover, the aromatic content of aerosol WSOC samples collected between autumn and winter seasons is higher (∼18–19%) than that of samples collected during warmer periods (∼6–10%). The presence of aromatic signals typical of lignin-derived structures in samples collected during low-temperature conditions highlights the major contribution of wood burning processes in domestic fireplaces into the bulk chemical properties of WSOC from aerosols. According to our investigations, aerosol WSOC hydrophobic acids and aquatic fulvic and humic acids hold similar carbon functional groups; however, they differ in terms of the relative carbon distribution. Elemental analysis indicates that H and N contents of WSOC hydrophobic acids samples surpass those of aquatic fulvic and humic acids. In general, the obtained results suggest that WSOC hydrophobic acids have a higher aliphatic character and a lower degree of oxidation than those of standard fulvic and humic acids. The study here reported suggests that aquatic fulvic and humic acids may not be good models for WSOC from airborne particulate matter.     

Pentachlorophenol association with fulvic acids from recycled wastes

The apparent water solubility of pentachlorophenol was measured at pH=6 and at 25 degrees C in pure water, aqueous solutions of three salts (NaCl, KNO(3) and CaCl(2) at 0.010, 0.10 and 1.0M) and in aqueous solutions of three fulvic acids samples extracted from a natural soil (sFA), composted sewage sludge (csFA) and composted livestock's material (lsFA). A solubility enhancement method was developed for the measurement of partition coefficients (K(oc), L/kg organic carbon). Pentachlorophenol associates strongly with the fulvic acid samples and the calculated K(oc) were the following (averages and standard deviations): (sFA) (211+/-22) x 10(2), (csFA) (253+/-26) x 10(2), (lsFA) (235+/-10) x 10(2). For comparison purposes the K(oc) for pyrene were also calculated for the three FA samples and were the following: (sFA) (119+/-10) x 10(2), (csFA) (239+/-21) x 10(2), (lsFA) (92+/-10) x 10(2). The analysis of variance (one-way ANOVA) of the effect of the type of FA sample on the solubilization of pentachlorophenol and pyrene shows that this factor causes significant differences on the aqueous solubilization of these two organic substances.     

Charge characteristics of humic and fulvic acids: comparative analysis by colloid titration and potentiometric titration with continuous pK-distribution function model

Charge characteristics of humic and fulvic acids of a different origin (inshore soils, peat, marine sediments, and soil (lysimetric) waters) were evaluated by means of two alternative methods - colloid titration and potentiometric titration. In order to elucidate possible limitations of the colloid titration as an express method of analysis of low content of humic substances we monitored changes in acid-base properties and charge densities of humic substances with soil depth, fractionation, and origin. We have shown that both factors - strength of acidic groups and molecular weight distribution in humic and fulvic acids - can affect the reliability of colloid titration. Due to deviations from 1:1 stoichiometry in interactions of humic substances with polymeric cationic titrant, the colloid titration can underestimate total acidity (charge density) of humic substances with domination of weak acidic functional groups (pK>6) and high content of the fractions with molecular weight below 1kDa.     

Removal of organic polyelectrolytes and their metal complexes by adsorption onto xonotlite

Natural organic polyelectrolytes (humic and fulvic acids) and their metal complexes were removed by adsorption onto xonotlite. The removal percentages of humic and fulvic acids by xonotlite were approximately 80% and 30%, respectively. Humic acid removal from solution by adsorption onto xonotlite took place more readily than fulvic acid removal. The molecular weight distributions of the humic substances remaining in solution after adsorption with the xonotlite were measured with size exclusion chromatography. A comparison of molecular weight distributions demonstrated conclusively that large molecular weight components were adsorbed preferentially, indicating that adsorption efficiency depends on the number of functional groups of humic substances. Furthermore, the surface topography of the adsorbent was observed before and after adsorption by scanning electron microscopy. The calculated heat of adsorption was of 330 kJ mol(-1) which was evaluated from the Clapeyron-Clausius equation. Therefore, the adsorption type can be considered chemical. Since xonotlite can be easily synthesized and obtained at low cost, the adsorption method of humic and fulvic acids is superior to their precipitation.     

Characterization of dissolved organic matter using high-performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) with a multiple wavelength absorbance detector

High-performance liquid chromatography-size exclusion chromatography (HPLC-SEC) coupled with a multiple wavelength absorbance detector (200-445 nm) was used in this study to investigate the apparent molecular weight (AMW) distributions of dissolved organic matter (DOM). Standard DOM, namely humic acid, fulvic acid and hydrophilic acid, from the Suwannee River were tested to ascertain the performance and sensitivity of the method. In addition to four compounds groups: humic substances (Peak 1, AMW 16 kD), fulvic acids (Peak 2, AMW 11 kD), low AMW acids (Peak 3, AMW 5 kD), and low AMW neutral and amphiphilic molecules, proteins and their amino acid building blocks (Peak 4, AMW 3 kD), an new group that appears to include low AMW, 6-10 kD, humic substances was found based on investigating the spectra at various elution times. The spectroscopic parameter S_>365 (slope at wavelengths >365 nm) was determined to be a good predictor of the AMW of the DOM. The detector wavelength played an important role in evaluating the AMW distribution. For some fractions, such as the humic and low AMW non-aromatic substances, the error in measurement was ±30% as determined by two-dimensional chromatograms detected at an artificially selected wavelength. HPLC-SEC with multiple wavelength absorbance detection was found to be a useful technique for DOM characterization. It characterized the AMW distributions of DOM more accurately and provided additional, potentially important information concerning the properties of DOM with varying AMWs.     

Copper(II) complexation by humic and fulvic acids from pig slurry and amended and non-amended soils

The effect of the consecutive annual additions of pig slurry at rates of 0 (control), 90 and 150 m3 ha(-1) y(-1) over a 4-year period on the binding affinity for Cu(II) of soil humic acids (HAs) and fulvic acids (FAs) was investigated in a field plot experiment under semiarid conditions. A ligand potentiometric titration method and a single site model were used for determining the Cu(II) complexing capacities and the stability constants of Cu(II) complexes of HAs and FAs isolated from pig slurry and control and amended soils. The HAs complexing capacities and stability constants were larger than those of the corresponding FA fractions. With respect to the control soil HA, pig-slurry HA was characterized by a much smaller binding capacity and stability constant. Amendment with pig slurry decreased the binding affinity of soil HAs. Similar to the corresponding HAs, the binding affinity of pig-slurry FA was much smaller while that of amended-soil FAs were slightly smaller when compared to the control soil FA. The latter effect was, however, more evident with increasing the amount of pig slurry applied to soil per year and the number of years of pig slurry application.     

Copper binding by peat fulvic and humic acids extracted from two horizons of an ombrotrophic peat bog

We studied the binding of Cu(II) to humic acids and fulvic acids extracted from two horizons of an ombrotrophic peat bog by metal titration experiments at pH 4.5, 5.0, 5.5, and 6.0 and 0.1 M KNO3 ionic strength. Free metal ion concentrations in solution were measured using an ion selective electrode. The amounts of base required to maintain constant pH conditions were recorded and used to calculate H+/Cu2+ exchange ratios. The amount of Cu(II) bound to the humic fractions was greater than the amount bound to the fulvic fractions and only at the highest concentrations of metal ion the amount of Cu(II) sorbed by both fractions became equal. The proton to metal ion exchange ratios are similar for all humic substances, with values ranging from 1.0 to 2.0, and decreasing with increased pH. The amount of Cu(II) bound is practically independent of the horizon from which the sample was extracted. The results indicate that the humic substances show similar cation binding behaviour, despite the differences in chemical composition. The copper binding data are quantitatively described with the NICA-Donnan model, which allows to characterize only the carboxylic type binding sites. The values of the binding constants are higher for the humic acids than for the fulvic acids.     

Effects of oxalic acid on the regrowth of heterotrophic bacteria in the distributed drinking water

Three laboratory-scale water pipe systems were set up to study the effects of adding oxalic acid on the bacterial regrowth and biofilm formation in the distributed drinking water. The results of water pipe experiment displayed that around 38% carbon in the oxalic acid could be converted to bacterial biomass. The maximum HPCs in biofilm were equal to 3.5x10(4), 3.38x10(5) and 2.8x10(6) CFUcm(-2) while the maximum HPCs of free bacteria were equal to 1.2x10(3), 2.54x10(3) and 3.78x10(4) CFUml(-1) for the blank and with addition of 10 and 50 micrograms OA eq-Cl(-1), respectively. These results imply that the addition of oxalic acid to distributed water has positive effect on the assimilable organic carbon content of drinking water and bacterial regrowth in water pipe. This effect is enhanced with addition of high-level oxalic acid. Batch tests were also conducted using water samples collected from a Taiwanese drinking water distribution system. The bacterial regrowth potentials (BRPs) of the blank were equal to 4.25x10(3), 1.46x10(4), 4.9x10(4) and 7.54x10(4) CFUml(-1) for water samples collected from treatment plant effluent, commercial area, mixed area, and residential area, respectively. These results show that the biological stability of distributed drinking water is the highest in treatment plant effluent, the moderate in the commercial area and mixed area, and the lowest in the residential area.     

Fulvic and humic acids isolated from groundwater: Compositional characteristics and cation binding

Samples of humic substances were obtained from a waterworks at Fuhrberg, Germany. The material had a bimodal molecular size distribution with 40% of the total carbon in the 50,000–100,000-D (nominal molecular weight, NMW, in daltons) size fraction and 50% of the carbon in the <10,000-D (NMW) size fraction. The fulvic and humic acids isolated from the bulk humic substances were low in nitrogen content and had low H/C atomic ratios. Furthermore, the fulvic and humic acids had very similar elemental, spectral and copper binding characteristics. Over 70% of the carbon in both the fulvic and humic acids was present in aromatic or aliphatic groups, with ¹³C NMR analyses indicating approximately even distribution among the two types. Competitive elemental binding studies indicated that Ca²⁺, Mg²⁺, Al³⁺ and Fe³⁺ do not effectively compete for copper binding sites on these compounds. In humic acids, these cations are predominantly bond by carboxylic groups.     

Effects of copper on spore germination, growth and ultrastructure of Polypodium cambricum L. gametophytes

The effects of different concentrations (10(-5), 5x10(-5) and 10(-4)M) of copper bromide on spore germination, growth and ultrastructure were investigated in Polypodium cambricum L. gametophytes. The inhibitory effect of Cu was observed in spores cultured on medium supplemented with 10(-4)M CuBr(2): germination occurred about 40 days after sowing and was only 25%. Concentrations of 5x10(-5) and 10(-4)M CuBr(2) induced changes in gametophyte development, possibly by re-orientation of growth. Gametophytes treated with 10(-5) and 5x10(-5)M CuBr(2) took up and accumulated a large amount of copper and ultrastructural observations showed that cytoplasmic damage was limited to twisted swollen thylakoids. The ultrastructure of gametophytes treated with 10(-4)M CuBr(2) showed absence of a vacuolar compartment. The present observations suggest that P. cambricum gametophytes could be a suitable material for studying physiological and molecular alterations induced by excess copper.     

Photolysis of fluometuron in the presence of natural water constituents

Phototransformation of the herbicide fluometuron (1 microM) in natural sunlight was investigated in neutral Milli-Q water and in synthetic waters containing either fulvic acids, nitrate ions or both in order to mimic reactions taking place in aquatic environments. Fluometuron degradation followed a pseudo-first order kinetics. The reaction was faster in synthetic than in Milli-Q water. Fulvic acids (10 mg l(-1)) increased the rate of fluometuron photolysis by a factor 2.5 and nitrates (25 mg l(-1)) by a factor 15. Identification of major photoproducts was conducted under laboratory conditions using LC-ESI-MS. Numerous photoproducts were detected and tentatively characterized. In the presence of nitrates, hydroxylation of the aromatic ring with or without hydrolysis of CF(3) into CO(2)H and oxidation of the urea chain leading to demethylation were observed. In the presence of fulvic acids, hydroxylation of the aromatic ring was the major reaction route.     

The complexation of Cu(II) by anthropogenic fulvic acids extracted from composted urban and livestock wastes

Abstract

The fulvic acid (fua) fractions of two samples of composted solid wastes [urban (urfua) and livestock (lsfua) wastes], commercialized to be used in agriculture as organic correctives or fertilizers, were analyzed for their affinity towards Cu(II) at pH=6. Molecular fluorescence spectroscopy (synchronous mode) was used to monitor the quenching caused by the complexation upon addition of Cu(II) to fua. Spectral data were preprocessed by a chemometric self‐modeling mixture analysis method (SIMPLISMA) to detect the number of different types of fluorescent binding sites that exist in each fua, their spectra and the corresponding quenching profiles [fluorescence intensity as function of the total Cu(II) concentration]. From the analysis of the quenching profiles, the amount of binding sites (Cl) and the corresponding conditional stability constants (K') were calculated. Both fua samples have approximately Cl = 0.21 mmol/g and the logarithms of K’ are 4.21(3) and 4.51(8), respectively for urfua and lsfua. The differences detected between these fua samples and those extracted from natural soils can be attributed mainly to the relatively small humification extent of the present anthropogenic fua samples.     

Effect of preozonation on the characteristic transformation of fulvic acid and its subsequent trichloromethane formation potential: presence or absence of bicarbonate

The effects of bicarbonate on the characteristic transformation of fulvic acid (FA) and its subsequent trichloromethane formation potential (TCMFP) were investigated in the process of preozonation. Dissolved organic carbon (DOC) removal rate and the residual aqueous ozone concentration during preozonation were measured with different bicarbonate concentration. The presence of bicarbonate inhibited DOC removal and decreased TCMFP yields in the initial oxidation period. In order to explain these phenomena, the molecular weight (MW) distribution (<5, 5-10, 10-30, and >30 kDa) and corresponding TCMFP were investigated for FA and its subsequent oxidation products. Furthermore, transformation of molecular structure, based on MW distribution, was also characterized with Fourier transform infrared (FTIR) spectrum. Bicarbonate showed different inhibiting effects on TCMFP of organic species with different MW, and more significant TCMFP decrement was observed for the high MW fraction (>30 kDa) than for the low MW fractions. Preozonation led to obvious reduction on DOC and UV254 in most of MW fractions wherever bicarbonate was present or not, demonstrating that ozone contributed to both organics mineralization and structure variation, synchronously. As being indicated from the results of FTIR and gas chromatography-mass spectrometry, the functional groups such as alcohols, epoxides and phenols, the formation of which was promoted with hydroxyl radicals (.OH) and would be remarkably inhibited by bicarbonate, were responsible for the increment of TCM precursor's concentration during ozonation. Results of these studies confirmed low dosage bicarbonate affecting the ozonation pathways, influencing the intermediate species formation and impacting its subsequent TCMFP yields through inhibiting the .OH radicals reactions mainly occurred in high MW fractions.     

Heavy metal binding by the polymeric organic fractions of sewage sludges

Organic complexes in sewage sludge play an important role in the speciation and transformation of metals into potentially more toxic and bioavailable forms. Two organic fractions, bacterial extracellular polymer and fulvic acid, were extracted from mixed liquor and digested sewage sludge by methods established as the most appropriate. The homogeneity of the extracts was verified using gel permeation chromatography. Conditional stability constants and complexation capacities of the organic fractions from the sludges with copper, cadmium, nickel and zinc have been determined using equilibrium dialysis titration. Organic fractions extracted from digested sludge demonstrated a greater capacity to complex metals over mixed liquor extracts. Copper formed stronger complexes than nickel with the mixed liquor biomass and cadmium exhibited the greatest affinity for digested sludge organic matter.     

Predicting Pb bioavailability to freshwater microalgae in the presence of fulvic acid: algal cell density as a variable

In order to better understand the relationship between lead speciation and its bioavailability in natural waters, the interactions between Pb(II), fulvic acid and the freshwater alga, Chlorella kesslerii were studied at various algal cell densities. An increase in cellular lead or fulvic acid adsorbed to algae was observed with decrease of the cell density from ca. 10(7) to 10(5)cells ml(-1). In the presence of fulvic acid, cellular Pb was greater than that expected for the same free lead ion concentrations in the absence of fulvic acid in agreement to our previous study. This effect was found to be more pronounced at lower cell density, in accordance with increased fulvic acid adsorption to algae. Good fit between experimental observations and model predictions of cellular Pb at various cell densities, was observed by assuming that fulvic acid adsorbed to algae give rise to additional binding sites for Pb(II). The findings of this study indicate that a further extension of the biotic ligand model which includes the formation of a ternary complex and cell density (or concentration) as an input parameter is needed to improve its site-specific predictive capacity, especially in the case of dissolved organic matter-rich surface waters. This extension of predictive capacity would allow to reduce the deviations from the BLM model predictions for microalgae in the presence of dissolved organic matter and hence will serve as a mechanistic tool for establishing ambient site-specific water quality criteria.     

Separation and characterization of the colored material from sugarcane molasses

The colored material (X) was effectively separated from sugarcane molasses using reversed-phase chromatography. Characterization of the molecular structure of sample X was performed using infrared absorption (IR) spectrometry, mass spectrometry (MS), and dynamic light scattering (DLS). The IR spectrum was similar to that of commercial humic acid, and the MS analysis showed that the sample possessed relatively small heterogeneous molecules with molecular masses around 234, 446, 657, 868, and 1079 Da. On the other hand, X sample showed an inhibitory activity toward the cysteine proteinase papain. Furthermore, the inhibitory (G-1) and weak inhibitory (G-2) fractions were separated from sample X using gel permeation chromatography. Samples G-1 and G-2 inhibited papain partial-noncompetitively and had the inhibition constants of 5.01 x 10(-5) and 1.08 x 10(-3)M, respectively. Interestingly, in the DLS experiment, the Stokes radius of sample G-1 was approximately 2 nm, about twice one of sample G-2.     

Natural organic compounds as alternative to methyl bromide for nematodes control

Thirty-three organic acids and furfural metabolites were examined for their nematicidal activity against plant-parasitic, free-living and predacious nematodes. Propionic acid, 2-methylhexanoic acid, lactic acid, maleic acid, and furic acid were the most effective nematicides among normal chain organic acids, branched organic acids, hydroxy/keto-acids, dicarboxylic acids and furfural metabolites, respectively. Seven of the tested compounds were found to have more than 90% mortality thus designating them as highly active nematicides. Of the highly active tested compounds, an average octanol/water log P of 0.97 was observed with a range from 0.28 to 2.64, and a Henry's Law constant averaging 2.6 x 10(- 7) atm.m3/mole. Tested chemicals with minor or low nematicidal activity showed an average log P of 1.76 with a range from 0.15 to 3.42 and a Henry's Law constant averaging 16.6 x 10(- 7) atm.m3/mole.     

Hydrogen peroxide-assisted UV photodegradation of Lindane

Aqueous solutions of gamma-hexachlorocyclohexane (Lindane) were photolyzed (lambda=254 nm) under a variety of solution conditions. The initial concentrations of hydrogen peroxide (H(2)O(2)) and Lindane varied from 0 to 20 mM and 0.21 to 0.22 microM, respectively, the pH ranged from 3 to 11, and several concentration ratios of Suwannee River humic acid and fulvic acid were dissolved in the irradiated solutions. Lindane rapidly reacted, and the maximum reaction rate constant (9.7 x 10(-3) s(-1)) was observed at pH 7 and initial [H(2)O(2)]=1 mM. Thus, 90% of the Lindane is destroyed in approximately 4 min under these conditions. In addition, within 15 min, all chlorine atoms were converted to chloride ion, indicating that chlorinated organic by-products do not accumulate. The reactor was characterized by measuring the photon flux (7.04 x 10(-6) E s(-1)) and the cumulative production of *OH during irradiation. The cumulative *OH production during irradiation was fastest at an initial [H(2)O(2)]=5 mM (k=0.77 micro M s(-1)).