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.     

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.     

Organic compounds adsorption onto activated carbon: the effect of association between dissolved humic substances and pesticides

The quantitative determination of pesticide binding to dissolved humic substances is relevant to both water treatment operation using activated carbon adsorption process and the application of transport models that predict the environmental distribution patterns of a given hydrophobic contaminant. In this study and in a first set of experiments, the extent of binding between (i) three pesticides of environmental concern, aldicarb, lindane and pentachlorophenol, and (ii) dissolved commercial humic acid and soil extracted fulvic acid, was determined using dialysis experiments and water solubility enhancement tests. In a second set of experiments, the influence of dissolved humic substances or pesticide on the retention of the other co-adsorbate onto activated carbon was investigated in binary systems. It was found that association was negligible for aldicarb and that the pesticide sorption onto activated carbon was not affected by humic acid (8.5 mg liter(-1) DOC). The association constants K for lindane and pentachlorophenol were identical in the presence of fulvic acid (logK=4.1) but lower than that observed with humic acid. In the presence of humic acid, binding affinity for pentachlorophenol (logK=4.6) was higher than the one observed for lindane (logK=4.4), despite its much higher water solubility. This observation suggests that the aromatic character of the pentachlorophenol molecule contributes to association interactions with humic acid. From co-adsorption experiments onto activated carbon it was found that fulvic acid (7.7 mg litre(-1) DOC) slightly enhances sorption kinetics of pentachlorophenol. Lindane (1 mg litre(-1)) does not affect sorption kinetics for fulvic acid but markedly enhances both the sorption kinetics and adsorptive capacity for humic acid. Activated carbon retention of dissolved humic substances or pesticide appears to be enhanced by the association potential that exists between these co-adsorbates in some binary systems.     

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.     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

凹凸棒土对腐殖酸的低温吸附性能研究

首次研究凹凸棒土对饮用水中腐殖酸的低温吸附性能,考察5℃条件下,吸附时间与腐殖酸初始浓度、吸附剂投加量、pH对凹凸棒土吸附腐殖酸的影响,确定吸附剂的吸附等温线、吸附动力学和热力学等相关理论参数,研究凹凸棒土对腐殖酸的吸附性能与机理。结果表明,江苏盱眙凹凸棒土在温度5℃、pH=4、水中腐殖酸初始浓度为5 mg/L,投加量为15 g/L的条件下,吸附180 min后对腐殖酸的去除率可达97.26%。凹凸棒土对腐殖酸的吸附符合二级吸附动力学方程与Freundlich吸附等温式,吸附过程由孔隙内扩散过程控制,吸附为自发的吸热过程,包括物理吸附与化学吸附。根据Fre-undlich吸附等温式拟合计算,5℃、pH=7时理论最大吸附量为9 mg/g,说明凹凸棒土对于低温饮用水中腐殖酸具有良好的吸附效果。     

Sorption of humic substances on aquifer material at artificial recharge of groundwater

Experiments in batch equilibrium system were carried out to evaluate the importance of physical and chemical factors determining the sorption efficiency of humic substances (HS) on aquifer material, which has been used for artificial recharge of groundwater (ARG) in drinking water production. Results showed that an increase of the amount of clay in the aquifer material and a decrease of pH in water increased the sorption efficiency. The sorption of higher molecular weight, more hydrophobic and aromatic HS (Aldrich and forest soil humic acids) were greater than the sorption of acidic HS (river fulvic acids), either on the aquifer material or to its representative sorbing phases, clay and organic matter. The sorption on the aquifer material was largely due to physical sorption (hydrophobic attractions). This study showed the importance of HS composition on their removal during ARG and contributed to an understanding of the HS sorption mechanisms in this process.     

Determining the role of human substances in the fate of pesticides in the environment

The data presented in this paper emphasize that the behavior and fate of pesticides in the environment is influenced by humic substances. Various methods most frequently used for the characterization of humic substances are discussed. Both humic acid and fulvic acid can solubilize in water certain organic compounds and are important carriers of some pesticides in soil. Humic substances have the potential for promoting the nonbiological degradation of many pesticides. Several methods of bleaching humus color from drinking water, including chlorination, ozonation, and UV-radiation, are described. Finally, the photochemical stability to UV-radiation of certain pesticides in aqueous fulvic acid solution is discussed.     

Influence of dissolved humic substances on the leaching of MCPA in a soil column experiment

The influence of dissolved humic substances on the transport of (4-chloro-2-methylphenoxy) acetic acid (MCPA) in a sandy soil with a low organic carbon content was studied in a column experiment. Soil columns were eluted with aqueous solutions containing different fractions of humic substances. More than 70% of the applied compound was found in the leachate in all sandy soil experiments, but distinct differences were obtained depending on the composition of the eluent. The addition of both humic and fulvic acids to the eluent affected the leaching behaviour of MCPA. While the presence of humic acids increased and accelerated the movement of MCPA in the investigated sandy soil, fulvic acids caused the opposite effect: increased retention was observed relative to the control. We concluded that a possible carrier transport or retention strongly depends on the composition of the dissolved organic matter. Thus, changes in the composition of dissolved organic matter may affect MCPA movement into deeper soil layers.     

城市污水二级出水中溶解性有机物特性分析

分别采用凝胶色谱、亲疏水性组分分离、荧光色谱等方法,研究了城市污水处理厂二级出水中溶解性有机物的分子量分布、亲疏水组分含量以及荧光光谱特性。结果表明,二级出水中疏水性组分较亲水性组分多,疏水性组分约占总有机物的64.3%,而亲水性组分占35.7%左右;二级出水及其不同亲/疏水组分中溶解性有机物分子量分布基本集中在4.5 kDa以下,其中弱疏水性组分和亲水性组分中主要为分子量小于1.5 kDa的有机物;二级出水溶解性有机物中含有腐殖酸类、富里酸类以及蛋白质类物质,其中含量以腐殖酸类为主。     

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.     

Determining the role of humic substances in the fate of pesticides in the environment

Abstract

The data presented in this paper emphasize that the behavior and fate of pesticides in the environment is influenced by humic substances. Various methods most frequently used for the characterization of humic substances are discussed. Both humic acid and fulvic acid can solubilize in water certain organic compounds and are important carriers of some pesticides in soil. Humic substances have the potential for promoting the nonbiological degradation of many pesticides. Several methods of bleaching humus color from drinking water, including chlorination, ozonation, and UV‐radiation, are described. Finally, the photochemical stability to UV‐radiation of certain pesticides in aqueous fulvic acid solution is discussed.     

Montmorillonite-Cu(II)/Fe(III) oxides magnetic material as adsorbent for removal of humic acid and its thermal regeneration

In this work, the adsorption features of montmorillonite and the magnetic properties of Cu(II)/Fe(III) oxides were combined in a material to produce magnetic adsorbent, which can be separated from the medium by a simple magnetic process after adsorption. The magnetic material is effective for the removal of humic acid. At pH 6.1, 96% removal was observed from 4.4 mg l(-1) humic acid solution containing 0.02 M NaCl. The adsorption is pH and ionic strength dependent. Adsorption is favored at lower pH values and dissolved NaCl can enhance the adsorption. The adsorption mechanism of humic acid to the magnetic material was suggested to be the ligand exchange reaction between carboxylic groups of humic acid molecules and the magnetic material surface. The magnetic material can be thermally regenerated. The temperature and time required to achieve good regeneration efficiency were determined to be 300 degrees C and 3 h, respectively. The regenerated adsorbent is still magnetic and approximately has as high specific saturation magnetization and good adsorption capacities as the as-prepared adsorbent.     

Kinetics and mechanisms of interaction of simazine with humic acids

Abstract

The adsorption of simazine on two fractions of hu‐mic acids of different molecular size was investigated at a pH range of 2.5 to 6.2. The amounts of the herbicide adsorbed decreased with increasing pH for both of the two humic acids fractions used and no adsorption was observed at pH 5.5. The adsorption capacity of fraction I (M_v >100,000) exceeded that of fraction IV (M_v < 4,000) over the entire pH region used. No appreciable changes in the adsorbed amounts were observed after 24 hours.

Continuous flow dialysis techniques were used to determine the extent of binding between simazine and dissolved humic acids. It was observed that 50% and 60% of simazine added were thus removed from the dialysis bags containing humic acids fractions I and IV,respectively. Higher amounts of simazine were adsorbed by the high molecular weight humic fraction. The adsorption processes involve ionic bonds between simazine and humic acids. In addition it is likely that hydrogen bonds and physical forces are also involved in the adsorption of simazine by humic acids.     

Effects of aquatic humic substances on a hydrophobic ultrafiltration membrane

Natural humic surface water (pH 5.9), ion exchanged samples of the same water (pH 5.5), and aqueous solutions of isolated humic substances at pH 4.5, 5.5 and 6.5, respectively, were ultrafiltered (15°C, 0.5 bar) using hydrophobic polysulfone membranes (GR51) in a cross-flow flat sheet module. The used membrane did not completely retain natural organic matter from the surface water and the addition of complexing metals did not affect the retention any further. The changes which were induced in the membranes during each filtration run were studied by simultaneous streaming potential and flux measurements in 0.01 M KCl solutions. Zeta potentials were calculated based on the streaming potentials and the results showed changes towards more negative values for all the samples due to adsorption of organic matter onto the surface of the membrane pores. Humic acid affected the membrane charges more than fulvic acid. High ionic strength and low pH enhanced flux reduction and fouling. Filtration of natural waters caused more pore plugging and flux reduction than filtration of solutions of the isolated humic substances.     

Removal of humic substances from water by means of calcium-ion-enriched natural zeolites.

The ability of the natural zeolited Neapolitan Yellow Tuff (NYT) enriched with calcium ions to remove humic acids from water was evaluated by batch adsorption equilibrium tests and dynamic experiments carried out by percolating humic acid solutions through a small NYT column (breakthrough curves). Under the experimental condition explored, the sorption capacity increases with the ionic strength and has the highest value at pH 7.4. The partition coefficient for a low concentration of humic acid ([humic acid] --> 0), at pH 7.4 in 0.01 M sodium chloride, was approximately 1000 L/kg, versus the value of approximately 100 L/kg in the absence of the alkaline metal salt. Therefore, after humic acids have been adsorbed in a column filled with the calcium-ion-enriched tuff, a reduction of the salt concentration in the ongoing solution enhances the release of the adsorbed material. These findings show that NYT can be used for the removal of humic acids from water.     

Influence of humic substances on the toxic effects of cadmium and zinc to the green alga Pseudokirchneriella subcapitata

A method combining (1 h) algal photosynthesis inhibition tests and tangential-flow ultrafiltration (TFF) technique (cut-off 1 kDa) was used to determine the effect of humic substances (HS) on acute metal toxicity to Pseudokirchneriella subcapitata. Three "standard" HS (soil and peat humic acids and Suwannee River fulvic acids) at two concentrations (1 and 5 mg/l) and two metals (Zn at 390 microg/l and Cd at 200 microg/l) were studied. Toxicity of Cd and Zn to P. subcapitata was significantly (p<0.05) reduced in the presence of humic acids (HA) but not in the presence of Suwannee River fulvic acids (SRFA). Metal partitioning between colloidal (1 microm-1 kDa) and truly dissolved (<1 kDa) fractions was found to match a decrease of metal toxicity in the presence of HA, but not in the presence of SRFA. The results suggested that HA reduced Cd and Zn toxicity in two different ways: (1) HA decrease the amount of free metal ions. Metal-HA complexes are high molecular weight, relatively stable with regard to metal-exchange reactions and consequently the metals were less bioavailable. (2) HA adsorbed onto algal surfaces, shielded the cells from free Cd and Zn ions. Several possible explanations can be postulated to account for the observed SRFA results: (1) Cd- and Zn-SRFA complexes are thought to be labile (i.e. undergo rapid dissociation); (2) SRFA coagulated, presumably during equilibration, and that coagulation altered metal complexing behavior of SRFA; (3) FA has a lower ability to adsorb on cell membranes at pH>7.     

Competition between alga (Pseudokirchneriella subcapitata), humic substances and EDTA for Cd and Zn control in the algal assay procedure (AAP) medium

The chemical speciation of trace metals in natural waters has important implications for their biogeochemical behavior. Trace metals are present in natural waters as dissolved species and associated with colloids and particles. The complexation of one trace metal (Cd and Zn at 200 and 390 microg/l respectively) with a green alga Pseudokirchneriella subcapitata in colloid-free algal culture medium and in presence of colloidal humic substances (HS) is presented. The influence of the nature of colloids was also addressed using three "standard" HS: fulvic acid (FA) and, soil (SHA) and peat humic acids (PHA). The chemical speciation model, MINTEQA2, was used to simulate the influence of pH and standardized culture medium on metal association with humic substances. The model was successfully modified to consider the differences in the metal complexation with fulvic (FA) and humic acids (HA). The deviations of concentrations of metals associated with HS between experimental results and model predictions were within a factor of approximately 2. The results of speciation model highlight the influence of the experimental conditions (pH, EDTA) used for alga bioassay on the behavior of Cd and Zn. The computed speciation suggests working with a pH buffered/EDTA-free mixture to avoid undesirable competition effects. The behavior of Cd and Zn in solution is more strongly influenced by HS than by alga. Metal-HS associations depend on metal and humic substance nature and concentration. Cd is complexed to a higher extent than Zn, in particular at larger HS concentration, and the complexation strength is in the order FA相似文献   

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.