Decomposition Of Humic Acids Research Articles

Persistent free radicals in natural organic matter activated by iron particles enhanced disinfection byproduct formation

The widespread presence of iron (Fe) particles and natural organic matter (NOM) in drinking water distribution systems (DWDS) can significantly affect tap water quality, contributing to aesthetic issues and potentially generating harmful disinfection byproducts (DBPs). This study revealed that Fe particles, when combined with humic acid (HA), substantially increased DBP formation during chlorination. Fe particles (particularly preformed Fe particles) significantly increased haloacetic acid (HAA) formation by activating the persistent free radicals (PFRs) in the HA. Compared with the control system without Fe particles, greater than 2 times of HAA increase were observed for the system with Fe pariticles. PFRs accumulated on Fe particle surface could generate hydroxyl radicals, facilitating the decomposition of HA into smaller molecules, which were more reactive with chlorine disinfectants, thus elevated the DBP formation including both known and unknown N-DBPs and Cl-DBPs. The DBP promotion effect of in-situ formed Fe particles was much less than that of preformed Fe particles although both in-situ formed and preformed Fe particles could accumulate PFRs from HA. In-situ formed particles primarily accumulated carbon-centered PFRs, while preformed particles accumulated oxygen-centered PFRs. To mitigate the Fe particle induced water quality risks, it is crucial to control iron pipe corrosion and iron release in DWDS. In addtion, the optimization of treatment processes such as coagulation and filtration to more completely remove NOM and Fe particles could help minimize the DBP formation.

Extraction of humic acid from peat and lignite and the thermal behavior of their mixtures with ammonium nitrate

Due to the positive effect on soil structure and the influence on improving the efficiency of plant roots nutrient uptake, humic acids (HA) are widely considered for fertilizer production. Especially, it seems to be particularly promising to use them as additives in technologies of mineral fertilizer production. One of the common mineral fertilizer components, due to its good water solubility and the presence of nitrogen in two forms, is ammonium nitrate (AN). The aim of this study was to determine the influence of the humic acids extracted from peat and lignite on the thermal decomposition of HA and the thermal decomposition of ammonium nitrate and humic acids mixtures. For the quality assessment of HA, spectroscopic methods (FTIR/ATR and CP/MAS 13C NMR) and analysis of elemental composition were used. The analysis of the spectra showed differences in the degree of humification of humic acids extracted from various raw materials. HA isolated from peat were distinguished by the presence of peptides, polysaccharides, and lignin residues. Elemental analysis showed the higher carbon and sulfur content in the extracted HA compared to the reference samples. The results of the TG-DTA-MS analysis confirmed the influence of differences in the molecular structure of humic acids, especially in the aliphatic and aromatic carbon content, on the thermal decomposition process. Total content of carboxylic and/or hydroxylic functional groups had a significant impact on the start of the decomposition temperature. Their increase visibly influenced the acceleration of the exothermic decomposition of AN.

Effects of Heating on the Binding of Rare Earth Elements to Humic Acids

In deep underground environments, temperature is one of the key factors affecting the geochemistry behaviors of rare earth elements (REE) in organic-rich fluid. However, the influence of temperature on the interaction between humic acids (HA) and REE is not well known. In the present study, the influence of temperature on the HA–REE-binding behavior was evaluated based on heating experiments of REE-doped HA solution. Lignite-extracted HA and REE-binding experiments were conducted over a temperature range of 20 to 200 °C to quantify HA–REE complexation and the influence of temperature on HA binding sites. Results showed that increasing temperature and decreasing [REE]/[HA] ratio cause an increase of Kd value (the partition coefficient of REE between HA and aqueous solution). During heating KdREE KdREE patterns gradually change from middle REE-enriched-type (M-type) at 20 °C to light and middle REE-enriched-type (L-M-type) at 50 and 100 °C, and to light REE-enriched-type (L-type) at 150 °C and 200 °C. The increase of REE bonded with HA and modifications of KdREE patterns during the thermal treatment may be attributed to the increase of REE-binding sites, especially carboxylic sites, as a consequent of HA decomposition. This study provides a glimpse into the HA–REE-binding behaviors in the deep underground environment, which may shed light on the geochemical characteristics of REE in some organic-bearing rocks, and their changes during the coalification process.

Coupling photocatalytic and electrocatalytic oxidation towards simultaneous removal of humic acid and ammonia−nitrogen in landscape water

Aiming to bring photocatalytic and electrocatalytic oxidation processes into solving practical issue of organics and ammonia−nitrogen pollution in landscape water that resulting in algae bloom and eutrophication, this work firstly investigates photocatalytic oxidation of humic acid and electrochemical oxidation of ammonia upon optimization of each process parameters, respectively. The platinum modified titania (Pt/TiO2) exhibits improved activity than pure titania and CuOx, MnOx and NiOx modified titania for decomposition of humic acid. As an application−oriented study, this work has developed a simple and effective brushing and annealing method for immobilization of TiO2 and Pt/TiO2 onto ceramic foam for further application. In addition, the RuO2–IrO2/Ti electrode presents the best electrocatalytic activity compared with RuO2/Ti and IrO2/Ti electrodes in terms of ammonia oxidation, and the ammonia conversion pathways have been studied. Lastly, an integrated and enlarged reactor system employing optimized photocatalytic ceramic foam and stable electrodes has been developed for simultaneous oxidation of humic acid and ammonia−nitrogen in water circulated flow condition, based on cooperative production of reactive oxidant species between photocatalysis and electrocatalysis. The results show that coupled photocatalytic and electrocatalytic oxidation is a promising approach for treatment of organic matter and inorganic ammonia nitrogen in landscape water.

Thermal analysis of mechanochemically activated humic acids of brown coal

Humic acids of brown coal before and after mechanochemical treatment under various conditions were studied by TG and DSC (carried out both in air and in an inert atmosphere, with the temperature range of 300–800 K), and gel permeation chromatography. The obtained data were used to calculate the values of the energy of activation and the thermal effects for each stage of thermal decomposition. Influence of mechanochemical treatment upon humic acids thermolysis stages was shown. Hypothesis of thermal stages chemical interpretation was proposed. The staged decomposition of humic acids includes the stages of decarboxylation of acid groups of various types. A change in the staging of decomposition is observed upon mechanochemical introduction of alkali into humic acids, associated with the conversion of acid groups to the salt form.

Mechanisms of genuine humic acid evolution and its dynamic interaction with methane production in anaerobic digestion processes

Humic acid (HA), a byproduct formed during the biological conversion of organic matter into biogas in the anaerobic digestion (AD) process, contains complex structures and redox functions. However, the evolution mechanism of HA and its interaction with CH4 production during the AD process have not been fully explored, particularly with respect to various substrates and temperature conditions. In this study, we investigated the evolutionary dynamics of the structure and function of genuine HA that naturally formed in the AD processes of chicken manure and corn stover under mesophilic (37 °C) and thermophilic (55 °C) conditions. The results demonstrated that the HA evolution mechanisms in AD of chicken manure and corn stover have different pathways. The AD of core stover showed higher degree of aromaticity (41.2–66.7% and 45.3–68.4% for mesophilic and thermophilic respectively) and humification index (1.5–4.2 and 2.8–4.5 for mesophilic and thermophilic respectively) than those (28.3–45.3% and 30.2–54.5% of aromaticity and 0.6–1.2 and 1.3–3.7 of humification index) in AD of chicken manure. The results from HSQC NMR spectroscopy and 2D-COS-FTIR spectroscopy demonstrated an accelerating effect of the higher temperature on the evolution of HA through humification. Moreover, the concurrent decomposition and re-polymerization of HA during both AD processes, resulting in positive and negative effects on CH4 production in the fast and slow CH4 production stages, respectively. The dynamic interaction was due to variations in the electron transferring ability and structure of the formed HA. The results could not only advance our understanding of the mechanisms of HA evolution and its interaction with the performance of AD process, but also support further research toward improving AD performance by regulating HA formation and transformation.

Thermal degradation features of soil humic acid sub-fractions in pyrolytic treatment and their relation to molecular signatures

Pyrolysis is a promising treatment for soil remediation for rapidity and fertility preservation. But it is difficult to establish the relationship between pyrolysis behaviors and soil organic matter (SOM) structures, for SOM is a mixture of heterogeneous compounds. HA sub-fractions from the same soil source may provide a series of promising objects to understand SOM at molecular level and the resulting patterns in SOM pyrolysis. We first propose a novel insight into pyrolysis mechanism response to molecular signatures using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) combined with thermogravimetric analysis (TGA) to study six humic acid (HA) sub-fractions extracted from a forest soil. The findings indicate that decomposition of soil HA occurs systematically due to molecular signatures. The decomposition can be categorized as carboxyl controlled (below 280 °C), lipid-dominated (280–450 °C) and condensed aromatics-dominated processes (450–700 °C). Predominant reaction mechanism of all HA sub-fractions was random nucleation (α > 0.25). Lipid in HA tend to initiate multiple nuclei in thermal degradation, while condensed aromatics tend to initiate and grow centering single random point in higher conversion rate (α > 0.75). Bridging the molecular signature and thermogravimetry reveals that the pyrolysis stage below 350 °C should be divided into two distinct processes related to the carboxylic group and lipid compounds, although this stage has conventionally been considered as a single process. The N element of HA was mostly preserved in the condensed aromatics which was mainly pyrolyzed above 450 °C, suggesting that pyrolysis below 450 °C is a preferable remediation treatment considering nitrogen fertility preservation. The observed molecular-level pyrolysis patterns can be applied as a targeted remediation procedure for contaminated soils and can improve the understanding of SOM thermal behaviors at the molecular level.

Decomposition of humic acid by ozone: oxidation properties and water-matrix constituents

Decomposition of humic acid by ozone: oxidation properties and water-matrix constituents

Humic Acids Isolated from Selected Soils from the Russian Arctic and Antarctic: Characterization by Two-Dimensional 1H-13C HETCOR and 13C CP/Mas NMR Spectroscopy

Here we describe the molecular composition and resistance to decomposition of humic acids isolated from selected soils of the Russian Arctic and Antarctic. The degree of soil organic matter stabilization was assessed using modern instrumental methods: nuclear magnetic resonance spectroscopy (cross peak magic-angle spinning (CP/MAS) 13C-NMR and 1H-13C heteronuclear-correlation (HETCOR)). Analysis of the humic acids showed that aromatic compounds prevail in the organic matter formed in cryoconites, located on the surfaces of the glaciers. The predominance of aliphatic fragments is revealed in the soils of the Yamal peninsula and Antarctica. This could be caused by sedimentation of fresh organic matter exhibiting low decomposition stage due to the severe climate and processes of hydrogenation in the humic acids, destruction of the C-C bonds, and formation of chains with high hydrogen content. These processes result in formation of aliphatic fragments in the humic acids.

Humic acids adsorption and decomposition on Mn2O3 and α-Al2O3 nanoparticles in aqueous suspensions in the presence of ozone

The removal and decomposition of humic acids (HAs) in the presence of ozone and aqueous suspensions of Mn2O3 and α-alumina (Al2O3) nanoparticles was investigated. Mn2O3 presented lower BET specific surface area (15.6 m2 g−1 vs 45.8 m2 g−1) but a higher point of zero charge (PZC) (5.9 vs 4.2) than α-Al2O3. Solution pH played a key role in the adsorption of HAs and catalytic oxidation on the surface of α-Al2O3 and Mn2O3 nanoparticles. The adsorption capacity of α-Al2O3 at the natural pH of HAs in water (pH 5.5) was up to 2.903 gHAs g−1, but no adsorption occurred onto the Mn2O3 nanoparticles, due to the unfavorable surface charge at pH 5.5. In consequence, although Mn2O3 was a more efficient catalyst (khet = 0.7 L−1 min−1 g−1) than α-Al2O3 (khet = 0.2 L−1 min−1 g−1) for the decomposition of O3, Mn2O3 did not exhibited catalytic action during the ozonation of HAs at pH 5.5. Instead, the Mn2O3 catalytic action was significant at pH equal to PZC (catalytic rate constant ratio k1-HAcat/ k1-HA = 1.562). Overall, α-Al2O3 exhibited the highest catalytic removal rate of HAs during ozonation (k1-HAcat/ k1-HA = 2.298) due to favorable surface charge and larger specific surface area. The main mechanism for HAs removal in the presence of α-Al2O3 involves simultaneous adsorption of both HAs and O3, the reaction of ozone from the bulk solution and the catalytic decomposition of HAs on the solid surface by ROS, through complex series-parallel reactions. The α-Al2O3 dosage up to 0.5 g L−1 required to remove HAs by catalytic ozonation was significantly lower than in other studies employing granular activated carbon, iron coated zeolite or γ-alumina catalysts.

Method of Correlation Coefficient Optimization Used in UV-vis Spectrophotometric Analysis for Effluent in Catalytic Ozonation

A wavelength selection method for spectrophotometric analysis, named correlation coefficient optimization (CCO), was employed for reagent-free analysis of organics (humic acid) in real sewage. The modeling set of CCO uses the effluent in the ozonation process of humic acid (HA) solution. In order to verify the relationship between HA concentration and absorbance at the selected wavelength, HA solutions with different mass concentrations were prepared as a validation set. The study showed that the absorbance at 300 nm could be a good quantitative indication of HA concentration. In addition, the absorbance at 300 nm was applied to analyze the HA concentration in the ozonation process. The decomposition of HA fits the pseudo-first-order kinetic model and has a linear relationship with pH and (T – 20)2 (T is reaction temperature).

Laccase Production and Humic Acids Decomposition by Microscopic Soil Fungi

Laccase (para-diphenol:oxygen oxidoreductase, EC 1.10.3.2) is a phenol oxidase widespread in fungi and bacteria. In basidiomycetes, this enzyme is involved in the transformation of lignin and humic substances (HS) in soil. The role of laccases of soil ascomycetes and deuteromycetes in HS degradation is not established, and conditions of the enzyme production have been poorly studied. In the present work soil micromycetes, potential laccase producers, were isolated from typical soils of the forest, steppe, and foreststeppe zones of European Russia by plating on agar media with ABTS (2,2'-azino-bis(3-ethylbenzothiazoline- 6-sulphonic acid, sodium salt)) as the substrate. Their abundance, species composition, conditions of laccase production, and its relation to humic acids (HA) degradation in liquid and solid media were studied. Out of 68 strains isolated, 20 exhibited ABTS oxidation at initial plating on agar media. In pure cultures on agar media, oxidation was less pronounced, but in the presence of HA laccase production by some strains was higher than without HA. Significant and weak extracellular laccase production in liquid medium was observed for Acremonium murorum (Corda) W. Gams Z1710 and Botritis cinerea Pers. ex Fries Z1711, respectively. The level of laccase production by A. murorum was the same without inducers and in the presence of HA, while B. cinerea produced laccase only without inducers. No direct correlation was found between the presence of laccase and/or its activity and ability of the fungi to decolorize (degrade) HA. In liquid media active laccase producer A. murorum caused lower HA decolorization (43%) than B. cinerea (62%) and the fungi lacking extracellular laccase (54–81%). The role of micromycete oxidative systems in HA degradation requires further investigation.

Titanium silicalite-1 grafted with carbon nitride as carrier for cerium oxide-catalyzed ozonation of carboxylic acid in water

Humic acid (HA) can be rapidly decomposed in single ozonation (SOZ); however, it undergoes incomplete degradation and inefficiency in abatement of the total organic carbon (TOC) is observed. In this study, titanium silicalite-1 grafted with carbon nitride was used as a carrier for cerium oxide (Ce-O/C3N4@TS-1), and this catalyst led to more rapid and thorough decomposition of HA in water. The TOC removal efficiencies of HA solution were 20% in SOZ against 62% in catalytic ozonation (COZ) after 60 min of reaction. Furthermore, in order to investigate the reasons for increasing degree of mineralization, in this study, the catalytic effect of the catalyst toward ozonation of oxalic acid (OA) was also investigated. The results showed that Ce-O/C3N4@TS-1 not only presented a good catalytic activity, but also exhibited an excellent stability. The good activity was attributed to the presence of Ce redox pair (Ce3+/Ce4+) on its surface and generation of hydroxyl radicals which has a rapid reaction rate with OA. C3N4 provide a large scaffold for anchoring Ce-O, which was responsible for the favorable stability.

Utilization of pyrogallol in flotation separation of scheelite from calcite

ABSTRACT Scheelite is a typical tungsten-containing mineral and usually co-exists with calcite in deposits. The flotation separation of scheelite from calcite is a hard work in mineral processing. In this paper, pyrogallol, a by-product of humic acid decomposition was utilized as a depressant in flotation separation of scheelite from calcite. Flotation tests on singe mineral and mixed binary mineral were conducted. The results show that using pyrogallol as depressant can realize the flotation separation of scheelite from calcite by controlling pulp pH in 7.0–8.5. Zeta potential measurements and FTIR studies were performed to define the depression mechanism of pyrogallol on calcite. The results show that the pyrogallol depresses calcite flotation through complex adsorption and H bond adsorption on calcite surface.

A comparative study of ozonation, iron coated zeolite catalyzed ozonation and granular activated carbon catalyzed ozonation of humic acid

This study compares ozonation (O3), iron coated zeolite catalyzed ozonation (ICZ–O3) and granular activated carbon catalyzed ozonation (GAC–O3) for removal of humic acid from an aqueous solution. The results were evaluated by the removal of DOC that specifies organic matter, UV254 absorbance, SUVA (Specific Ultraviolet Absorbance at 254 nm) and absorbance at 436 nm. When ozonation was used alone, DOC removal was 21.4% at an ozone concentration of 10 mg/L, pH 6.50 and oxidation time of 60 min. The results showed that the use of ICZ or GAC as a catalyst increased the decomposition of humic acid compared to ozonation alone. DOC removal efficiencies were 62% and 48.1% at pH 6.5, at a catalyst loading of 0.75 g/L, and oxidation time of 60 min for ICZ and GAC, respectively. The oxidation experiments were also carried out using <100 kDa and <50 kDa molecular size fractions of humic acid in the presence of ICZ or GAC. Catalytic ozonation also yielded better DOC and UV254 reduction in both <50 kDa and <100 kDa fractions of HA compared to ozonation.

The effects of soil sand contents on characteristics of humic acids along soil profiles

It is generally accepted that the compositions and properties of soil organic matter (SOM) are influenced by many factors. In order to reveal the effects of soil texture on characteristics and dynamics of SOM and its sub-fraction, humic acid (HA), along two soil profiles, a yellow soil profile and a purplish soil profile, under the same climate and vegetation conditions were determined. Results indicate that the decomposition and humification degrees of SOM and HA of the purplish soils are higher than those of the corresponding yellow soils indicated by A/O–A ratios of HAs, TOCs and HA yields of bulk soil samples, nevertheless, the development degree of the purplish soil is lower than that of the yellow soil. The variations of E4/E6 ratios of HAs along the soil profiles indicate the overall molecular sizes of HAs decreased downward along the soil profiles. A/O–A ratios of HAs decreased downward along both the soil profiles indicate that humification processes decrease downward along both the soil profiles. Leaching of SOM shows significant effects on the distribution and characteristics of HAs in the yellow soil profile but the purplish soil profile, which is consistent with the higher hydrophobicity of HAs in purplish soils, shows that the distribution characteristics of SOM along the soil profiles are a complex result of the combination of soil texture and characteristics of SOM itself. The remarkably different sand contents are concluded tentatively as one of reasons to the different distributions and dynamics of HAs along the soil profiles, however, to profoundly understand the evolution and transport of SOM along soil profiles needs more researches.

The influence of feed composition on fouling and stability of a polyethersulfone ultrafiltration membrane in a photocatalytic membrane reactor

The investigations on the influence of humic acids (HAs) being representatives of Natural Organic Matter (NOM) and inorganic salts (NaHCO3, Na2HPO4 and Na2SO4) representing inorganic ions in natural waters, on fouling and stability of a polyethersulfone ultrafiltration membrane in a photocatalytic membrane reactor (PMR) are reported. The influence of inorganic ions on the permeate flux was dependent on their concentration and was more significant at higher salts content. The HCO3− ions contributed to the permeate flux decline to the highest extent, which was attributed to both a higher feed pH and a formation of a dense fouling layer. In the presence of SO42− the permeate flux was higher than in case of other ions which was explained in terms of lower thickness of the fouling cake caused by repulsion of TiO2 particles by the membrane under such conditions. The most severe decrease of the permeate flux observed in the presence of a mixture of HAs and inorganic salts was attributed to the formation of a thick fouling cake caused by bridging effect between HAs molecules and TiO2 particles under high ionic strength conditions. The inorganic salts contributed also to a decrease of HAs decomposition rate due to the hole and hydroxyl radicals scavenging effect of the ions. It was found that the conditions prevailing in the PMR contributed to the loss of the membrane separation properties towards dextrans due to the abrasive action of TiO2 particles. However, the extent of the observed decrease in the dextrans rejection was dependent on the feed composition.

Anaerobic decomposition of humic substances by Clostridium from the deep subsurface.

Decomposition of humic substances (HSs) is a slow and cryptic but non-negligible component of carbon cycling in sediments. Aerobic decomposition of HSs by microorganisms in the surface environment has been well documented; however, the mechanism of anaerobic microbial decomposition of HSs is not completely understood. Moreover, no microorganisms capable of anaerobic decomposition of HSs have been isolated. Here, we report the anaerobic decomposition of humic acids (HAs) by the anaerobic bacterium Clostridium sp. HSAI-1 isolated from the deep terrestrial subsurface. The use of 14C-labelled polycatechol as an HA analogue demonstrated that the bacterium decomposed this substance up to 7.4% over 14 days. The decomposition of commercial and natural HAs by the bacterium yielded lower molecular mass fractions, as determined using high-performance size-exclusion chromatography. Fourier transform infrared spectroscopy revealed the removal of carboxyl groups and polysaccharide-related substances, as well as the generation of aliphatic components, amide and aromatic groups. Therefore, our results suggest that Clostridium sp. HSAI-1 anaerobically decomposes and transforms HSs. This study improves our understanding of the anaerobic decomposition of HSs in the hidden carbon cycling in the Earth’s subsurface.

Comparison of UV/hydrogen peroxide and UV/peroxydisulfate processes for the degradation of humic acid in the presence of halide ions.

This study compared the behaviors of two classic advanced oxidation processes (AOPs), hydroxyl radical-based AOPs ((•)OH-based AOPs) and sulfate radical-based AOPs (SO4 (•-)-based AOPs), represented by UV/ hydrogen peroxide (H2O2) and UV/peroxydisulfate (PDS) systems, respectively, to degrade humic acid (HA) in the presence of halide ions (Cl(-) and Br(-)). The effects of different operational parameters, such as oxidant dosages, halide ions concentration, and pH on HA degradation were investigated in UV/H2O2/Cl(-), UV/PDS/Cl(-), UV/H2O2/Br(-), and UV/PDS/Br(-) processes. It was found that the oxidation capacity of H2O2 and PDS to HA degradation in the presence of halides was nearly in the same order. High dosage of peroxides would lead to an increase in HA removal while excess dosage would slightly inhibit the efficiency. Both Cl(-) and Br(-) would have depressing impact on the two AOPs, but the inhibiting effect of Br(-) was more obvious than that of Cl(-), even the concentration of Cl(-) was far above that of Br(-). The increasing pH would have an adverse effect on HA decomposition in UV/H2O2 system, whereas there was no significant impact of pH in UV/PDS process. Furthermore, infrared spectrometer was used to provide the information of degraded HA in UV/H2O2/Cl(-), UV/PDS/Cl(-), UV/H2O2/Br(-), and UV/PDS/Br(-) processes, and halogenated byproducts were identified in using GC-MS analysis in the four processes. The present research might have significant technical implications on water treatment using advanced oxidation technologies.

Insights into the role of humic acid on Pd-catalytic electro-Fenton transformation of toluene in groundwater.

A recently developed Pd-based electro-Fenton (E-Fenton) process enables efficient in situ remediation of organic contaminants in groundwater. In the process, H2O2, Fe(II), and acidic conditions (~pH 3) are produced in situ to facilitate the decontamination, but the role of ubiquitous natural organic matters (NOM) remain unclear. This study investigated the effect of Aldrich humic acid (HA) on the transformation of toluene by the Pd-based E-Fenton process. At pH 3 with 50 mA current, the presence of HA promoted the efficiency of toluene transformation, with pseudo-first-order rate constants increase from 0.01 to 0.016 as the HA concentration increases from 0 to 20 mg/L. The HA-enhanced toluene transformation was attributed to the accelerated thermal reduction of Fe(III) to Fe(II), which led to production of more hydroxyl radicals. The correlation of the rate constants of toluene transformation and HA decomposition validated hydroxyl radical (·OH) as the predominant reactive species for HA decomposition. The finding of this study highlighted that application of the novel Pd-based E-Fenton process in groundwater remediation may not be concerned by the fouling from humic substances.