The role of humic substances in chromium sorption onto natural organic matter (peat)

To elucidate mechanisms of Cr³⁺ sorption onto the unaltered solid natural organic matter, the comparative studies of this ion binding from a solution at pH 4.0 onto three selected particle size fractions: 2000–1000 μm, 630–200 μm and 63–20 μm of markedly different HS content and structure, separated by a wet sieving from an overall sample of peat (Brushwood Peat Humus) were carried out. Comparable patterns of COOH groups and CEC_t confirmed that for cation exchange capacity were responsible mainly cations connected with COO⁻ functional groups. It was though found that aliphatic acids in the solid state did not take part in Cr³⁺ binding, thus the finest studied fraction 63–20 μm of the highest contents of functional groups showed the lowest sorption capacity for Cr³⁺, while similar patterns of sorbed Cr³⁺, soluble HS content and base CEC₀ indicated that these parameters were directly interrelated. The base ion exchange processes determined by CEC₀ (with Ca²⁺ as a predominant exchangeable cation) appeared to be not the major mechanisms responsible for Cr³⁺ sorption. For this metal, strong binding to insoluble large molecular weight organic pool two- to threefold prevailed over the ion exchange processes. Very low acid desorption indicated generally low mobility of Cr³⁺-organic compounds.     

Effect of soil amendments on sorption and mobility of metribuzin in soils

Metribuzin (4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one), is weakly sorbed to soil therefore, leaches easily to lower soil profiles. Soil amendments play a significant role in the management of leaching losses of pesticides. Therefore, present study reports the effect of organic manure and fly ash amendments on metribuzin downward mobility in sandy loam soil columns. Application of animal manure [T-1(OM) and T-2(OM)] and fly ash [T-1(FA) and T-2(FA)] at 2.5% and 5.0% levels increased the metribuzin retention in the soil. Freundlich constant [K(f)(1/n)] values of metribuzin for treatments T-1(OM) and T-2(OM) were 0.70 and 1.11, respectively, which were significantly higher than the value (0.27) in natural soil (T-0). The respective values for treatments T-1(FA) and T-2(FA) were 1.80 and 4.61. Downward mobility of metribuzin was studied in packed soil columns [300 mm (l)x59 mm (i.d.)]. Both the amendments significantly reduced the downward mobility of metribuzin and affected breakthrough time and maximum concentration of metribuzin in the leachate. Leaching losses of metribuzin were decreased from 97% in natural soil (T-0) column to 64% [T-1(OM)] and 42% [T-2(OM)] for animal manure-amended columns and 26% [T-1(FA)] to 100% [T-2(FA)] for fly ash-amended columns, as metribuzin did not leach out of 5% fly ash-amended column. Study indicates that both animal manure and fly ash were quite effective in reducing the downward mobility of metribuzin in packed soil columns of a sandy loam soil.     

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.     

Influence of dissolved humic substances on the mass transfer of organic compounds across the air-water interface

The effect of dissolved humic substances (DHS) on the rate of water-gas exchange of two volatile organic compounds was studied under various conditions of agitation intensity, solution pH and ionic strength. Mass-transfer coefficients were determined from the rate of depletion of model compounds from an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution (dynamic system). Under these conditions, the overall transfer rate is controlled by the mass-transfer resistance on the water side of the water-gas interface. The experimental results show that the presence of DHS hinders the transport of the organic molecules from the water into the gas phase under all investigated conditions. Mass-transfer coefficients were significantly reduced even by low, environmentally relevant concentrations of DHS. The retardation effect increased with increasing DHS concentration. The magnitude of the retardation effect on water-gas exchange was compared for Suwannee River fulvic and humic acids, a commercially available leonardite humic acid and two synthetic surfactants. The observed results are in accordance with the concept of hydrodynamic effects. Surface pressure forces due to surface film formation change the hydrodynamic characteristics of water motion at the water-air interface and thus impede surface renewal.     

Effects of pollution on humic substances

To assess effects of industrial and environmental pollution on analytical characteristics of humic substances, we isolated humic acids (HA's) and fulvic acids (FA's) from unpolluted and polluted soils and sediments. Following purification, the HA's and FA's were characterized by elemental (C, H, O, N, S) and functional group (CO2H, phenolic OH, total acidity) analyses, infrared (IR) spectrophotometry, differential thermal analysis (DTA) and by metal (Fe, Al, Cu, Mn, Pb, Ni, Co, Zn, Cr, Cd, Hg, Ca and Mg) analyses. Si was also determined in all samples. Polluted HA's and FA's contained more N and S but less O and were richer in all metals and Si than were unpolluted ones. IR spectra showed that polluted humic materials were enriched in COO- groups, secondary non-cyclic amides and possible also in SO3H groups. DTA curves indicated that polluted HA's and FA's were more thermostable than unpolluted HA's and FA's. Unusually high N, S, Cu, Cr, Zn and Hg contents of humic materials appear to be useful indicators of soil and sediment pollution.     

Effects of pollution on humic substances

Abstract

To assess effects of industrial and environmental pollution on analytical characteristics of humic substances, we isolated humic acids (HA's) and fulvic acids (FA's) from unpolluted and polluted soils and sediments. Following purification, the HA's and FA's were characterized by elemental (C, H, O, N, S) and functional group (CO₂H, phenolic OH, total acidity) analyses, infrared (IR) spectrophotometry, differential thermal analysis (DTA) and by metal (Fe, Al, Cu, Mn, Pb, Ni, Co, Zn, Cr, Cd, Hg, Ca and Mg) analyses. Si was also determined in all samples.

Polluted HA's and FA's contained more N and S but less 0 and were richer in all metals and Si than were unpolluted ones. IR spectra showed that polluted humic materials were enriched in COO^‐ groups, secondary non‐cyclic amides and possible also in SO₃H groups. DTA curves indicated that polluted HA's and FA's were more thermostable than unpolluted HA's and FA's. Unusually high N, S, Cu, Cr, Zn and Hg contents of humic materials appear to be useful indicators of soil and sediment pollution.     

Contributions of humic substances to the dissolved organic carbon pool in wetlands from different climates

Wetlands are an important source of DOM. However, the quantity and quality of wetlands' DOM from various climatic regions have not been studied comprehensively. The relationship between the concentrations of DOM (DOC), humic substances (HS) and non-humic substances (NHS) in wetland associated sloughs, streams and rivers, in cool temperate (Hokkaido, Japan), sub-tropical (Florida, USA), and tropical (Sarawak, Malaysia) regions was investigated. The DOC ranged from 1.0 to 15.6 mg CL(-1) in Hokkaido, 6.0-24.4 mg CL(-1) in Florida, and 18.9-75.3 mg CL(-1) in Sarawak, respectively. The relationship between DOC and HS concentrations for the whole sample set was regressed to a primary function with y-intercept of zero (P<0.005) and a slope value of 0.841. A similar correlation was observed between DOC and NHS concentrations, with a smaller slope value of 0.159. However, the correlation coefficient of the latter was much larger when the data was regressed to a logarithmic curve. These observations suggest the presence of a general tendency that the increased DOC in the river waters was mainly due to the increased supply of HS from wetland soils, whereas the rate of the increase in the NHS supply has an upper limit which may be controlled by primary productivity.     

Comparison of photochemical behavior of various humic substances in water: III. Spectroscopic properties of humic substances

Spectral absorption coefficients and fluorescence quantum efficiencies were determined for humic substances from a variety of sources. Specific absorption coefficients k_h, for humic substances at wavelengths λ from 300 to 500 nm can be closely described by the relation Ae^B(450-λ), where A and B are constants. When the k_h values are in units of liter (mg organic carbon)^?1meter^?1 and wavelength λ is in nanometers, mean values of A and B for aquatic humus in the 12 water bodies studied were 0.6±0.3 and 0.014±0.001, respectively. Spectral absorption coefficients of dissolved organic matter in blackwater rivers, of the “yellow substance” in the sea, and of fulvic acids extracted from soils are very similar. Fluorescence quantum yields of humic substances were low and more variable than the absorption coefficients, ranging from 0.0005 to 0.012 with excitation at 350 nm (average of 0.0045±0.0038 for 6 waters). Fluorescence spectra for the humic substances were remarkably similar with maximum emission at 430 to 470 nm. Results of this study can be used to compute photolysis rates of pollutants as a function of depth in natural water bodies.     

Effect of complexation with humic substances on diffusion of metal ions in water

Most studies on diffusion of metal ions in various water-rock systems have dealt with free ions (hydrated ions). However, it is often the case that metal ions are dissolved as complexed species such as with humic substances (HS) in natural waters. Hence, we need to study the diffusion behavior of these complexes in order to understand fully the diffusion phenomenon in natural. In this study, the diffusion coefficients of free metal ions (M(z+)) and their complexes with HS (M-HS) were compared to understand the effect of complexation with HS on the diffusion of metal ions such as Co(2+), Cd(2+), and rare earth elements (REE(3+)). Although the diffusion coefficients of free metal ions depend on ionic potential, such dependence was not observed in the presence of HS. Comparing the diffusion coefficients of metal complexes with ethylenediaminetetraacetate (EDTA), fulvic acid, and humic acid showed that the molecular weight (MW), or the size of the ligand, is of primary importance for the diffusion of M-HS. As a consequence, the diffusion coefficients of all REE(3+) were similar in the presence of HS, while they were different in the absence of HS due to the different size of each REE(3+). The similarity among the diffusion coefficients of REE-HS was caused by the much larger size of HS compared with each ion. However, the distribution coefficients of M-HS were not similar among REE(3+), Cd(2+), and Co(2+). REE(3+) and Cd(2+) which have higher affinities for larger MW fraction in HS diffused slower than Co(2+) which favors smaller MW fraction. The results show that the affinity for different MW fractions among HS controls the diffusion of M-HS, which must be important to predict precisely the diffusion behavior of metal ions bound to HS in natural systems.     

Effect of humic substances on the Fenton treatment of wastewater at acidic and neutral pH

This paper describes results of treatability studies of the effect of humic substances (humate, HS, at the concentration 500-5000 mg l-1) on the Fenton (Fe2+/H2O2) treatment of industrial wastewater at pH 3.5 and 7.0. Without humate, the removal of all contaminants was significantly higher at pH 3.5 than at pH 7. At pH 7.0, the removal of all compounds in the presence of HS (3000 mg l-1) was comparable to that at pH 3.5 without HS. At pH 3.5, humate had no effect on the removal of arsenic, thiocyanate and cyanide, but the removal of all organic compounds (phenol, 2,4-dimethylphenol, benzene, toluene, o-xylene, m- & p-xylene and dichloromethane) was significantly inhibited. Mechanisms of the processes are discussed. It is suggested that, in the presence of HS, acidification of the treated wastewater may not only be unnecessary but it can even hinder the degradation of organic pollutants.     

Photocatalytic oxidation of toxic organohalides with TiO2/UV: the effects of humic substances and organic mixtures

TiO2/UV photocatalytic oxidation of DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane), 1,2,3-trichlorobenzene and 4-chlorophenol were examined in aqueous solution in the presence of humic substances and organic mixtures to study if the degradation rates were affected. Both commercial and natural humic substances were observed to retard the photodegradation rates, with a greater effect from the natural humic substances. Acetonitrile and isopropanol also caused significant retardation of 4-chlorophenol photodegradation. The overall retardation can be attributed to the combination of light attenuation, inhibition and competition effects. Moreover, the TiO2/UV system favors the decomposition of compounds that have stronger adsorption onto the TiO2 surface. To engineer effective treatment facilities that use the TiO2/UV system for the treatment of toxic substances in wastewater, the methodology must allow for concerns about adventitious species which are present.     

Selectivity in the complexation of actinides by humic substances

The interactions of a range of actinide elements (Th, U, Np, Pu, Am) with humic substances from the Needle's Eye natural analogue site were studied by gel permeation chromatography. Bulk humic substances were isolated by ammonia extraction, followed by dialysis against distilled water and freeze-drying. The gel permeation results suggest that Needle's Eye humic substances can be fractionated into three incompletely resolved fractions with average molecular weights determined by analytical ultracentrifugation around 49 000 for Fraction 1, around 14 700 for Fraction 2 and around 8000 for Fraction 3. Although there are significant differences between the organic matter elution patterns in individual gel permeation experiments, presumably due to differences in column packing, these are much smaller than the differences between metal ions. The uranium that is naturally present in these humic substances is largely bound in the late-eluting fraction. Spikes of the early actinides, including Np and Pu in controlled valency states, have been added to the humic substances, and gel permeation of the spiked humic substances shows that the three humic fractions vary greatly in their effectiveness and selectivity as ligands for early actinides.     

Occurrence and distribution of organic trace substances in waters from the Three Gorges Reservoir, China

This study deals with the evaluation of water quality of the Three Gorges Reservoir (TGR) in order to assess its suitability as a raw water source for drinking water production. Therefore, water samples from (1) surface water, (2) tap water, and (3) wastewater treatment plant effluents were taken randomly by 2011–2012 in the area of the TGR and were analyzed for seven different organic contaminant groups (207 substances in total), applying nine different analytical methods. In the three sampled water sources, typical contaminant patterns were found, i.e., pesticides and polycyclic aromatic hydrocarbons (PAH) in surface water with concentrations of 0.020–3.5 μg/L and 0.004–0.12 μg/L, disinfection by-products in tap water with concentrations of 0.050–79 μg/L, and pharmaceuticals in wastewater treatment plant effluents with concentrations of 0.020–0.76 μg/L, respectively. The most frequently detected organic compounds in surface water (45 positives out of 57 samples) were the pyridine pesticides clopyralid and picloram. The concentrations might indicate that they are used on a regular basis and in conjunction in the area of the TGR. Three- and four-ring PAH were ubiquitously distributed, while the poorly soluble five- and six-ring members, perfluorinated compounds, polychlorinated biphenyls, and polybrominated diphenyl ethers, were below the detection limit. In general, the detected concentrations in TGR are in the same range or even lower compared to surface waters in western industrialized countries, although contaminant loads can still be high due to a high discharge. With the exception of the two pesticides, clopyralid and picloram, concentrations of the investigated organic pollutants in TGR meet the limits of the Chinese Standards for Drinking Water Quality GB 5749 (Ministry of Health of China and Standardization Administration of China 2006) and the European Union (EU) Council Directive 98/83/EC on the quality of water intended for human consumption (The Council of the European Union 1998), or rather, the EU Directive on environmental quality standards in the field of water policy (The European Parliament and The Council of the European Union 2008). Therefore, the suggested use of surface water from TGR for drinking water purposes is a valid option. Current treatment methods, however, do not seem to be efficient since organic pollutants were detected in significant concentrations in purified tap water.     

Influence of sorption to dissolved humic substances on transformation reactions of hydrophobic organic compounds in water. Part II: hydrolysis reactions

The effect of dissolved humic acid (HA) on two types of hydrolysis reactions was investigated: (I) dehydrochlorination of gamma-hexachlorocyclohexane (HCH) and 1,1,2,2-tetrachloroethane (TeCA) as a reaction involving hydroxide ions (OH(-)) and (II) hydrolysis of 1-octyl acetate (OA) which is catalyzed by H(+) at the applied pH value (pH 4.5). The rate of TeCA hydrolysis was not affected by addition of 2 g l(-1) of HA at pH 10 (k' = 0.33 h(-1)) but HCH hydrolysis was significantly inhibited (k' = 4.6 x 10(-3) h(-1) without HA and 2.8 x 10(-3)h(-1) at 2 g l(-1) HA). HCH is sorbed by 51% whereas TeCA sorption is insignificant at this HA concentration. Sorbed HCH molecules are effectively protected due to electrostatic repulsion of OH(-) by the net negative charge of the HA molecules. In contrast, OA hydrolysis at pH 4.5 (k' = 1.6 x 10(-5) h(-1)) was drastically accelerated after addition of 2 g l(-1) HA (k' = 1.1 x 10(-3) h(-1)). The ratio of the pseudo-first-order rate constants of the sorbed and the freely dissolved ester fraction is about 70. H(+) accumulation in the microenvironment of the negatively charged HA molecules was suggested to contribute to the higher reaction rate for the sorbed fraction in case of this H(+)-catalyzed reaction. Analogous effects from anionic surfactants are known as micellar catalysis.     

Comparison of photochemical behavior of various humic substances in water: I. Sunlight induced reactions of aquatic pollutants photosensitized by humic substances

Humic substances are shown to photosensitize transformations of several types of synthethic chemicals that do not photoreact when exposed to sunlight in distilled water. In most cases, photoproducts were the same in colored natural waters and in solutions of soil-derived humic substances, including those obtained commercially. Kinetic studies in sunlight indicated that the efficiencies of the reactions photosensitized by humic substances of various origins were the same within a factor of 2.     

A new approach to data evaluation in the non-target screening of organic trace substances in water analysis

Non-target screening via high performance liquid chromatography-mass spectrometry (HPLC-MS) has gained increasingly in importance for monitoring organic trace substances in water resources targeted for the production of drinking water. In this article a new approach for evaluating the data from non-target HPLC-MS screening in water is introduced and its advantages are demonstrated using the supply of drinking water as an example. The crucial difference between this and other approaches is the comparison of samples based on compounds (features) determined by their full scan data. In so doing, we take advantage of the temporal, spatial, or process-based relationships among the samples by applying the set operators, UNION, INTERSECT, and COMPLEMENT to the features of each sample. This approach regards all compounds, detectable by the used analytical method. That is the fundamental meaning of non-target screening, which includes all analytical information from the applied technique for further data evaluation. In the given example, in just one step, all detected features (1729) of a landfill leachate sample could be examined for their relevant influences on water purification respectively drinking water. This study shows that 1721 out of 1729 features were not relevant for the water purification. Only eight features could be determined in the untreated water and three of them were found in the final drinking water after ozonation. In so doing, it was possible to identify 1-adamantylamine as contamination of the landfill in the drinking water at a concentration in the range of 20 ng L⁻¹. To support the identification of relevant compounds and their transformation products, the DAIOS database (Database-Assisted Identification of Organic Substances) was used. This database concept includes some functions such as product ion search to increase the efficiency of the database query after the screening. To identify related transformation products the database function “transformation tree” was used.     

Influence of humic substances on the photolysis of aqueous pesticide residues

The present work investigated the direct and indirect photolysis of pesticide residues (atrazine, imazaquin, iprodione), in aqueous solutions and under UV-visible radiation (280-480nm). Different kinds of humic substances (HS) were added to samples in order to evaluate their behaviour as possible photocatalysts and their effect on the photolysis of pesticides. The fulvic acids were purchased from the International Humic Substances Society, and they were added to samples in concentrations ranging from 1 to 150 mgl(-1). Titanium dioxide was used as the photocatalyst, in concentration ranging from 10 to 150 mgl(-1). Pesticides photolysis were measured by UV-visible absorption spectroscopy and differential pulse polarography with all used pesticides, reaching total degradation after 2h of irradiation, thus indicating a fast direct photolysis. Photocatalysis by TiO(2) could increase the pesticides photolysis rate up to 40%. This effect, however, was not observed for imazaquin photolysis. Again, except for imazaquin, HS presence showed a positive effect in increasing pesticide degradation, but only within specific concentration ranges (below 10mg l(-1) for iprodione and about 30mgl(-1) for atrazine). Above these ranges HS induce a decrease in the pesticides photolysis rate. Spin-trapping measurements by electronic paramagnetic resonance spectroscopy, using the spin-trap DMPO, showed that HS are able to photogenerate hydroxyl radicals, increasing the pesticides molecule degradation. However, the HS also react with the photogenerated hydroxyl radical, influencing the pesticide photolysis, leading to a decrease in the photolysis rate and causing it to be strongly dependent on the nature and concentration of residues in the water to be treated.     

Accumulation of metals,trace elements and semi-volatile organic compounds on exterior window surfaces in Baltimore

Organic films have been found to develop on window surfaces [Diamond et al., Environmental Science and Technology 34 (2000a) 2900]. The film contains organic compounds that are in dynamic equilibrium with the gas-phase in air, and organic and inorganic compounds and elements associated with deposited air particles. In this study, the exterior surfaces of windows were sampled in downtown and suburban Baltimore, Maryland. Higher concentrations of PCBs, PAH, metals and trace elements were found at downtown than a suburban site. PCBs in the films at downtown sites were dominated by penta and hexa homologue groups and PAH signatures resembled that of vehicle emissions. Twenty-six metals and trace elements were separated into two groups according to their enrichment factors (EF). Ag, Hg, Se, Sb and Zn had EF > 100, suggesting anthropogenic sources of these metals in the films; whereas Fe, Ca, Co, Cr and others had EF <10, suggesting a crustal origin. An unusual profile dominated by deca- and nona- PCBs and relatively higher concentrations of Ag, Hg and Zn may be attributable to emissions from a medical waste incinerator. Dry deposition fluxes of selected metals on windows were 1.4-94 times higher on windows with than without films, indicating that the film increases the dry deposition of particles and their associated chemicals. This implies that film development, which is associated with elevated VOC and SOC emissions to urban air, will increase film development that will, in turn, increase the accumulation of other atmospherically deposited constituents such as metals.     

The influence of organic matter on sorption and fate of glyphosate in soil - Comparing different soils and humic substances

Soil organic matter (SOM) is generally believed not to influence the sorption of glyphosate in soil. To get a closer look on the dynamics between glyphosate and SOM, we used three approaches: I. Sorption studies with seven purified soil humic fractions showed that these could sorb glyphosate and that the aromatic content, possibly phenolic groups, seems to aid the sorption. II. Sorption studies with six whole soils and with SOM removed showed that several soil parameters including SOM are responsible for the strong sorption of glyphosate in soils. III. After an 80 day fate experiment, ∼40% of the added glyphosate was associated with the humic and fulvic acid fractions in the sandy soils, while this was the case for only ∼10% of the added glyphosate in the clayey soils. Glyphosate sorbed to humic substances in the natural soils seemed to be easier desorbed than glyphosate sorbed to amorphous Fe/Al-oxides.     

Sorption of selected pharmaceuticals by a river sediment: role and mechanisms of sediment or Aldrich humic substances

Environmental Science and Pollution Research - Sorption of pharmaceuticals onto sediments is frequently related to organic matter content. Thus, the present work aimed to compare the effect of...