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Determination of soluble aluminium concentration in alkaline humic water using atomic absorption spectrophotometry.

The steps of the standard method to determine soluble aluminium concentration are filtering, followed by acidifying, then analysing with the atomic absorption spectrophotometer (AAS). When applied to alkaline humic water, acidification gives rise to the formation of humic acid as a brown particulate matter. Of the total soluble aluminium in the original water, 49-61% forms complexes with the particulate humic acid upon acidification. Although the AAS is capable of detecting the binding aluminium, the particulate nature of humic acid easily induces inaccurate readings as a result of the non-uniform distribution of the particulate matter. A more precise analysis of soluble aluminium concentration of alkaline humic water is shown to be achievable in basicified solutions instead. Basicified solutions keep humic acid in the soluble form; hence maintain the homogeneity of the sample.

Aluminum↗

Adsorption of lead and humic acid on chitosan hydrogel beads.

Chitosan hydrogel beads were studied for the adsorption of lead ions and humic acid from aqueous solutions to examine the adsorption behaviors and mechanisms. The experiments were carried out at room temperature with solution pH ranging from 5 to 7.5 (in near neutral pH range). Three types of batch adsorption experiments, including single species adsorption, sequential adsorption of one species after another and co-adsorption of both species, were investigated. The results show that: (1) adsorption of either species mainly results from the complexations between adsorbate and functional groups at the surface of the hydrogel beads; (2) previously adsorbed species can either act as additional binding sites for, or occupy the same binding sites as the subsequent species to be adsorbed, resulting in enhanced or retarded adsorption of the subsequent species; and (3) for co-adsorption, metal-organic interactions play a very important role in determining the extent of adsorption. It is concluded that multi-species adsorption can be significantly affected by adsorbate interactions and the understanding of these interactions needs great attention in adsorption study in the future.

Adsorption↗

Steady-state humic-acid-containing blanket in upflow suspended bed.

We investigated the effects of turbidity and concentration of humic acid on the steady-state behavior of the blanket, which was coagulated using polyaluminum chloride (PACl) as coagulant. The three-dimensional solid-flux plot was constructed. Based on fixed PACl dosage, the iso-humic-acid solid-flux surfaces stacked that enveloped the feasible regime for the blanket bed. The steady-state point moved toward low solid flux and low solid fraction regime with decreasing initial raw water turbidity and/or increasing humic-acid concentration. Low water turbidity and high humic-acid concentration yielded a bulky blanket, with the former producing clean, and the latter turbid effluent. The presence of humic acid was thereby harmful to blanket strength, except for the case of low raw water turbidity. An optimal range of humic acid for blanket strength and clarification efficiency existed at 1 mg l(-1). Low level of humic acid is beneficial to blanket development with low-turbidity raw water.

Aluminum Chloride↗

Performance of selected anion exchange resins for the treatment of a high DOC content surface water.

The objective of this study was first to compare the performance of four strong anion exchange resins (AERs) (MIEX from Orica Pty Ltd, DOWEX-11 and DOWEX-MSA from DOW chemical and IRA-938 from Rohm and Haas) for their application in drinking water treatment (natural organic matter (NOM), mineral anions (nitrate, sulfate and bromide) and pesticide removal) using bench-scale experimental procedures on a high DOC content surface water. The efficiency of MIEX for NOM and mineral anions removal was furthermore evaluated using bench-scale dose-response experiments on raw, clarified and post-ozonated waters. NOM removal was assessed using the measurement of dissolved organic carbon (DOC), UV absorbance at 254 nm (UV254) and the use of high-performance size exclusion chromatography with UV (HPSEC/UV) and fluorescence detection (HPSEC/FLUO). The MIEX and IRA938 anionic resins exhibit a faster removal of NOM and mineral anions compared to the DOWEX11 and MSA AERs. All the resins were found to be very effective with similar performances after 30 to 45 min of contact time. As expected, only limited sorption of atrazine and isoproturon (C0=1 microg/L) occurred with MIEX, DOWEX11 and MSA AERs. MIEX resin proved to be very efficient in eliminating NOM of high-molecular weight but also a large part of the smallest UV absorbing organic compounds which were refractory to coagulation/flocculation treatment. Remaining DOC levels after 30 min of contact with MIEX were found similar in raw water, clarified water and even post-ozonated water implying no DOC benefit can be gained by employing conventional treatment prior to MIEX treatment. Removal of bromide (initial concentration 110 microg/L) was also observed and ranged from 30% to 65% for resin dose increasing from 2 to 8 mL/L. T

Adsorption↗

Effect of humic acid on the photolysis of the pesticide atrazine in a surfactant-aided soil-washing system in acidic condition.

The photolytic destruction of Atrazine (ATZ) following a surfactant-aided soil-washing process was investigated in the presence of humic acid (HA). A non-ionic surfactant, Brij 35, was found to be a good solving agent, extracting ATZ without causing any retardation effect on the photolysis process. However, the HA that was co-extracted from the surfactant-aided soil-washing system was found to be capable of improving the photolysis of ATZ at low concentrations, while quenching the photodegradation of ATZ at higher concentrations. By considering the light attenuation effect due to surfactant and HA, the quantum yields of the system with respect to the proposed reaction mechanisms of the associated excited states of ATZ were investigated and modeled. The relative kinetic rates of the dominant reaction mechanisms (i.e., deactivation of triplet, direct photolysis of triplet, product formation, and quenching of triplet) were then compared.

Atrazine↗

Dechlorination of tetrachloroethylene by palladized iron in the presence of humic acid.

The dechlorination of tetrachloroethylene (PCE) by palladized irons in the presence of humic acid was investigated to understand the feasibility of using Pd/Fe for the in situ remediation of contaminated groundwater. Untreated zerovalent iron (ZVI) was amended with Pd(II) ions to form palladized irons. X-ray photoelectron spectroscopy showed that Pd(II) was completely reduced to metallic Pd on the surface of ZVI. PCE was catalytically dechlorinated via beta-elimination to ethane and ethylene by palladized irons. The carbon mass balances were in the range of 78--98%. The dechlorination followed the pseudo first-order rate equation and the normalized surface reaction rate constant (k(sa)) for PCE dechlorination was 33.47+/-7.21 L/m(2)h in the absence of humic acid. Humic acid competed the reactive sites on the palladized irons with PCE, and thus lowered the dechlorination efficiency and rate of PCE. After 24h of equilibrium between humic acid and palladized irons prior to the injection of PCE, however, the efficiency and rate of PCE dechlorination could increase with increasing concentrations of humic acid. Addition of quinones having low redox potentials including AQDS, lawsone and hydroquinone also enhanced the dechlorination efficiency of PCE after 24h, depicting that humic acids serve as the electron shuttles to effectively transfer electrons and to accelerate the dechlorination efficiency and rate of PCE.

Humic Substances↗

Inactivation of particle-associated viral surrogates by ultraviolet light.

This study investigated whether colloid-sized particles can enmesh and protect viruses from 254-nm ultraviolet (UV) light and sought to determine the particle characteristics (e.g. size, chemical composition) that are most relevant in causing a protective effect. Two viral surrogates (MS2 coliphage and bacteriophage T4), three types of particles (kaolin clay, humic acid powder, and activated sludge), two coagulants (alum and ferric chloride), two filtration conditions (none and 0.45 microm), and two UV doses (40 and 80 mJ/cm2 for MS2 coliphage; 2 and 7 mJ/cm2 for bacteriophage T4) were considered in a series of bench-scale UV collimated beam experiments. Transmission electron microscopy was used to qualitatively confirm the phage particle-association after coagulation. Humic acid and activated sludge floc particles shielded both viral surrogates to a statistically significant degree (with >99% confidence) relative to particle-free control conditions, while the kaolin clay particles provided no significant protection. The results of the study suggest that particles <2 microm in diameter are large enough to protect viruses from UV light and that particulate chemical composition (e.g. UV-absorbing organic content) may be a critical factor in the survival of particle-associated viruses during UV disinfection.

Alum Compounds↗

Effect of humic acids on heavy metal removal by zero-valent iron in batch and continuous flow column systems.

The effects of Aldrich humic acids (HA) on the removal of Zero-valent iron (ZVI) was investigated in laboratory systems. In batch, the removal rate of Zn and Ni (5 mg l(-1)) was, respectively, 2.8 and 2.4 times lower in the presence of HA (20 mg l(-1)) than in the absence of HA, presumably due to the formation of HA-heavy metal complexes which prevented the removal reactions at the ZVI surface. Chromate removal was not affected. In a column test, two parallel systems were supplemented with a continuous input of simulated groundwater containing a mixture of the heavy metals Zn, Ni and Cr(VI) (5 mg l(-1) each), with or without HA (at 20 mg l(-1)). Initially, the two column systems efficiently (>90%) removed the heavy metals from the simulated groundwater. When the input heavy metal concentration was increased to 8-10 mg l(-1), a significant breakthrough of Ni and Zn, up to 80%, occurred in the column system fed with HA. Chromate and HA did not significantly break through. After 60 weeks, the effect of HA on leaching of the accumulated metals (approx. 2 mg g(-1)) was investigated. No significant leaching was observed. The results of this study suggest that the impact of dissolved organic matter on the efficiency and lifetime of a ZVI barrier for in situ removal of heavy metals should be considered in the design of the barrier.

Adsorption↗

Characterization of sewage plant hydrocolloids using asymmetrical flow field-flow fractionation and ICP-mass spectrometry.

Asymmetrical flow field-flow fractionation (AF4) was applied to characterize aquatic colloids from biological sewage plants and to infer information of colloidal loads, sources, and sinks within the plants, resp. the colloidal interaction with the aqueous phase and the sewage sludge. To characterize the colloids further, especially the distributions of colloid associated heavy metals, the AF4 system was coupled to an inductively coupled plasma mass spectrometer (ICP-MS). The size distribution is determined by AF4 with UV absorbance and fluorescence detection after a calibration by monodisperse polystyrene sulfonate standards (PSS). Samples from different sewage plants and from different depths and locations within a plant were compared. The fulvic/humic acid fraction with a particle diameter d(p) < 10 nm appeared to be comparable in all samples and decreases only slightly along the plants, whereas larger colloids with d(p) > 10 nm almost completely passed into the sewage sludge. The concentrations of the initial colloidal heavy metals decreased along the plants.

Colloids↗

The occurrence and removal of phthalates in a trickle filter STW.

This study investigated the fate of phthalates in a trickle filter sewage treatment works. A wide variety of phthalates were researched of which only two were present in significant amounts. Mean concentrations of di-(2-ethylhexyl) phthalate (DEHP) and diethyl phthalate (DEP) measured throughout the system were 23.6 and 25.0 microg/l in raw sewage, 22.0 and 24.8 microg/l in primary, 14.6 and 0.60 microg/l in trickle filter, 18.6 and 0.10 microg/l in humus tank and 18.5 and 0.40 microg/l in reedbed effluents, respectively. Removal by the trickle filter was constantly high for DEP (94-99%) whereas DEHP was variable (<1-44%). Mean concentrations of DEHP and DEP in raw sludge were 30.2 and 1.60 microg/g dry wt, respectively. A mass balance for DEHP was calculated using data from field studies and estimates of sludge production at the works. The mass balance approach helped to provide information that could be used to improve the design and operation of sewage treatment works.

Filtration↗

Development and application of functional assays for freshwater dissolved organic matter.

A series of 11 standardised, reproducible, assays have been developed of physico-chemical functions of dissolved organic matter (DOM) in freshwaters. The assays provide quantitative information on light absorption, fluorescence, photochemical fading, pH buffering, copper binding, benzo(a)pyrene binding, hydrophilicity and adsorption to alumina. To obtain DOM for the assays, a 45 L sample of filtered freshwater was rotary-evaporated to reduce the volume to ca. 500 cm3. The concentrate was then passed through a strong cation exchanger, in the Na+ form, to remove alkaline-earth cations, and then through 0.7 and 0.2 microm filters. Eight samples, two each from a lake and three streamwaters, were processed. The yields of dissolved organic carbon (DOC) ranged from 70% to 107% (average 91%). The samples of DOM, stored in the dark at 4 degrees C, retained their functional assay characteristics for up to 7 months. When assaying the concentrates, parallel assays were performed with Suwannee River fulvic acid (SRFA), as a quality control standard. For most of the assays, the results for eight freshwater DOM samples are similar to those obtained with SRFA, the chief exception being the greater hydrophilicity of the DOM samples. For eight of the assays, variability among the DOM samples is significantly (p < 0.01) greater than can be explained by analytical error, i.e. by comparison with results for the SRFA quality standard; the three exceptional assays are photochemical fading, copper binding and benzo(a)pyrene binding. The two lakewater samples studied gave the most extreme assay results, probably because of the influence of phytoplankton-derived DOM. Significant correlations of hydrophilicity and adsorption with optical absorbance may mean that some DOM functional properties can be predicted from comparatively simple measurements.

Benzo(a)pyrene↗

Interaction of trace elements in acid mine drainage solution with humic acid.

The release of metal ions from a coal mining tailing area, Lamphun, Northern Thailand, is studied by leaching tests. Considerable amounts of Mn, Fe, Al, Ni and Co are dissolved in both simulated rain water (pH 4) and 10 mg L(-1) humic acid (HA) solution (Aldrich humic acid, pH 7). Due to the presence of oxidizing pyrite and sulfide minerals, the pH in both leachates decreases down to approximately 3 combined with high sulfate concentrations typical to acid mine drainage (AMD) water composition. Interaction of the acidic leachates upon mixing with ground- and surface water containing natural organic matter is simulated by subsequent dilution (1:100; 1:200; 1:300; 1:500) with a 10 mg L(-1) HA solution (ionic strength: 10(-3) mol L(-1)). Combining asymmetric flow field-flow fractionation (AsFlFFF) with UV/Vis and ICP-MS detection allows for the investigation of metal ion interaction with HA colloid and colloid size evolution. Formation of colloid aggregates is observed by filtration and AsFlFFF depending on the degree of the dilution. While the average HA size is initially found to be 2 nm, metal-HA complexes are always found to be larger. Such observation is attributed to a metal induced HA agglomeration, which is found even at low coverage of HA functional groups with metal ions. Increasing the metal ion to HA ratio, the HA bound metal ions and the HA entities are growing in size from <3 to >450 nm. At high metal ion to HA ratios, precipitation of FeOOH phases and HA agglomeration due to colloid charge neutralization by complete saturation of HA complexing sites are responsible for the fact that most of Fe and Al precipitate and are found in a size fraction >450 nm. In the more diluted solutions, HA is more relevant as a carrier for metal ion mobilization.

Coal Mining↗

AFM study on the sorbed NOM and its fractions isolated from River Songhua.

Natural organic matter (NOM) and its fractions from River Songhua were concentrated and fractionated with the reverse osmosis technology and XAD resin. With the purpose of exploring the adsorbed morphology of NOM and its fractions from a specific water source, the tapping-mode atomic force microscopy (TMAFM) was employed. The effect of solution properties (pH, Ca(2+)) on NOM microtopography was also verified. The results showed that NOM and its fractions displayed obviously diverse morphologies due to their different characteristics. The macromolecular compounds with large SUVA value were prone to adsorb on the mica surface. The particle-shaped NOM macromolecules were loosely adsorbed on the mica surface, and the molecular aggregation phenomena were proved to be ubiquitous in this experimental condition. With the increase of pH value, the surface coverage of mica decreased evidently. Spherical conformation with relatively smaller diameters was observed in the acidic condition compared with the neutral and basic condition. In the presence of 0.1 mol L(-1) NaCl, aggregation phenomena were observed in all pH conditions and obvious aggregates were presented with the addition of only 5 mmol L(-1) CaCl(2).

Adsorption↗

THM, HAA and CNCl formation from UV irradiation and chlor(am)ination of selected organic waters.

The formation of disinfection by-products (DBPs), including chloroform, dichloroacetic acid (DCAA), trichloroacetic acid (TCAA), and cyanogen chloride (CNCl) after sequential exposure of four organic waters to UV irradiation via either low- or medium-pressure lamps and free chlorine (or preformed monochloramine) under practical conditions was simulated. Statistically significant changes in the DBP formation from chlorination due to the additional UV irradiation are commonly observed under testing conditions, although some of these changes are not practically significant. The impacts from UV exposure were found to be most significant in chloroform formation (up to 40 microg/L) among the four tested DBPs. Organics from rivers were more sensitive to UV alteration than was the organic drawn from soil. This difference could not be explained by the specific UV absorbance (SUVA) values. In most cases, irradiation with the medium-pressure UV lamp gave similar or slightly larger changes in DBP yields, compared with the corresponding trials using the low-pressure lamp. Different application sequences could significantly change the relative quantities of DBPs but no general trend was identified. Case-specific evaluation of the formation of chloroform and CNCl is necessary.

Acetates↗

Photodegradation of estrone and 17beta-estradiol in water.

The TiO(2)-assisted photodegradation of two natural female hormones, estrone (E1) and 17beta-estradiol (E2), was investigated in two UV-photo-reactors, followed by solid-phase extraction and analysis by gas chromatography-mass spectrometry (GC-MS). The degradation of E1 and E2 in both reactors followed the pseudo-first-order kinetics. In reactor 1 (150W), 97% of compounds were degraded within 4h of irradiation. Even more rapid degradation was observed in reactor 2 (15W) where 98% of both compounds disappeared within 1h, due to the shorter wavelength of UV-light in reactor 2 (fixed at 253nm) than reactor 1 (238-579nm). The influences of different initial chemical concentrations, pH value, the presence of dissolved organic matter and hydrogen dioxide, and the catalyst concentration on the degradation rate of E1 and E2 in aqueous solutions were investigated. The results show that the extent of photo-induced degradation of E1 and E2 strongly depends on the water constituents in solution. The degradation rate was increased when pH value was increased from 2 to 7.6, beyond which the degradation rate started to decrease. The presence of humic acid enhanced the degradation of E1 and E2 in both reactors as a result of photosensitisation effect of humic acid chromophore. The degradation rate increased with an increase in H(2)O(2) concentration. The degradation rate was also enhanced by increasing catalyst concentration up to 2g/l. The findings therefore suggest that photocatalysis can be a very effective method of rapidly removing certain EDCs from water.

Estradiol↗

Mobility, bioavailability, and toxic effects of cadmium in soil samples.

Total concentration is not a reliable indicator of metal mobility or bioavailability in soils. The physicochemical form determines the behavior of metals in soils and hence the toxicity toward terrestrial biota. The main objectives of this study were the application and comparison of three approaches for the evaluation of cadmium behavior in soil samples. The mobility and bioavailability of cadmium in five selected soil samples were evaluated using equilibrium speciation (Windermere humic aqueous model (WHAM)), extraction procedures (Milli-Q water, DMSO, and DTPA), and a number of bioassays (Microtox, growth inhibition test, contact toxicity test, and respiration). The mobility, represented by the water-extractable fraction, corresponded well with the amount of cadmium in the soil solution, calculated using the WHAM (r(2)=0.96, P<0.001). The results of the ecotoxicological evaluation, which represent the bioavailable fraction of cadmium, correlated well with DTPA extractability and also with the concentration of free cadmium ion, which is recognized as the most bioavailable metal form. The results of the WHAM as well as the results of extraction experiments showed a strong binding of cadmium to organic matter and a weak sorption of cadmium to clay minerals.

Adsorption↗

Trace metals in humic acids and their hydrolysis products.

The role of humic acids in the transport of trace elements in the Sava river biocycle (near Zagreb, Yugloslavia) has been investigated by means of neutron activation analysis. Humic acids can accumulate certain trace elements, but little is known about their selectivity under certain physicochemical conditions. Humic acids isolated from Sava river sediments were hydrolized to their main components, namely to amino acids (proteins), phenols (and phenolic acids), carbohydrates, polycyclic aromatics, and metals. Degradation of humic acids in the environment occurs by the action of microorganisms, and during this step, certain trace metals become available to Sava river animals through standard physiological processes. In this work neutron activation analysis was applied to the quantitative and qualitative determination of trace metals in humic acids of Sava river origin, and in their hydrolysis products. The trace metals measured were Ag, Fe, Co, Cs, Eu, Sb, Sc, Se, and Sr. The concentrations obtained ranged from 0.05 to 2730 micrograms of a certain microconstituent per gram of sample. The experimental data are compared with the laboratory experiments on the determination of stability constants for metal complexes of humic acids and their hydrolysis product. From these data it is possible to suggest the ecological importance of trace metals bonded to humic acids in a certain region. The results concerning the role of humic acids in the cycle of trace elements in Sava river biocycle are discussed.

Humic Substances↗