Water humic material

Under drinking water plant treatment conditions, humic materials and/ or resorcinol do not produce trihalomethanes with chlorine dioxide even when a slight excess of chlorine (1 percent to 2 percent) is present. Also, saturated aliphatic compounds are not reactive with chlorine dioxide. Alcohols are oxidized to the corresponding acids. 

A number of mathematical models have been developed in recent years which attempt to predict the behavior of organic water pollutants. >2>3 Models assume that compounds will partition into various compartments in the environment such as air, water, biota, suspended solids and sediment. The input to the models includes the affinity of the compound for each of the compartments, the rate of transfer between the compartments, and the rates of various degradation processes in the various compartments. There is a growing body of data, however, which indicates that the models to date may have overlooked a small but significant interaction. A number of authors have suggested that a portion of the compounds in the aqueous phase may be bound to dissolved humic materials and are not therefore truly dissolved. 

There is more current literature which speaks to exactly this point. Hassett -0 has found that the sorption of organic compounds from water to suspended particles is altered in the presence of dissolved organic carbon. Griffin Chian - - and Diachenko have found that the volatility of organic compounds in water decreases when humic materials are present. Perdue -2 has found that the rate of hydrolysis of the octyl ester of 2,4-D is decreased in the presence of humic materials. 

The third technique we used was a measurement of changes in the sorption behavior of a compound in the presence of humic materials. A thin film of OV-1, a methyl silicone gum used as a chromatographic stationary phase, was plated on the bottom of a 60 ml Hypo-Vial (Pierce Chemical Co., Rockford, 11.). A solution of radiolabeled pollutant was added to the vial in either buffered distilled water in a solution of humic materials. Again, it is assumed that the pollutant is solution consists of two fraction free and bound. It is also assumed... 

The difference between the concentration in the ultra-filtered water and the concentration inside the ultrafiltration cell is therefore a measure of the bound concentration. Griffin and Chian7-7-, Hassett 7-, and Diachenko have used volatilization measurements to determine the extent of binding of pesticides and pollutants to dissolved humic materials. In these experiments either the rate of gas stripping of a compound or its equilibrium vapor pressure is measured in the presence and absence of humic materials. The results obtained can be manipulated in such a way to determine the percentage of the pollutant bound. 

There is a body of data in the literature which indicates that dissolved humic materials may play a significant and previously overlooked role in the behavior of organic water pollutants. It has been shown that dissolved humic materials can affect degradation rates and phase transfer rates for a number of compounds. A number of methods have been developed in this research and by other researchers which can make quantitative measurements of the extent of binding between organic water pollutants and dissolved humic materials. Hopefully these methods will be used by other researchers to gain more insight into this phenomenon. 

The data presented here indicates that the extent of binding for a particular compound is related to the octanol/water partition coefficient for that compound. This is very similar to the sorption of compounds from water to sediment. Compounds with log Kow values less than four (such as Lindane) will probably not be bound to an appreciable extent in the environment. Compounds with very high log Kow values (DDT and DEHP) may be bound to a significant extent. The extent of binding will depend on both the concentration of humic material and on the nature of the humic material. The humic materials used in this research showed dramatically different affinities for DDT. The reasons for this are poorly understood and deserve further study. 

Hot water-extractable C accounts for 1-5% of soil organic C (Leinweber et al. 1995 Sparling et al. 1998 Chan and Heenan 1999) and about 50% of this is thought to be present as carbohydrate (Haynes 2005). Because it is usually extracted from air-dried soils much of the pool originates from desiccated microbial cells but it also includes exocellular polysaccharides, root exudates, lysates and humic material (Redl et al. 1990 Leinweber et al. 1995 Sparling et al. 1998). Both hot water extractable C (Sparling et al. 1998 Chan and Heenan 1999) and hot water-extractable carbohydrate (Ball et al. 1996 Haynes and Beare 1997 Debrosz et al. 2002) have been used as indices of soil quality. 

Sposito, G. (1986), "Sorption of Trace Metals by Humic Materials in Soils and Natural Waters", CRC Crit. Rev. Environ. Control 16, 193-229. 

Humic residues occur in soil, fresh-water and sea-water. In soils these humic materials represent the principal organic residue of mature soils and are recognised as consisting of three principal components ... 

Humic materials are partially soluble in water and thus occur in both surface and groundwaters. 

A fractionation procedure has been established and widely applied to studies of humic materials [42-44]. The procedure begins with natural OM (i.e., humus) and uses an aqueous basic solution (e.g., 0.1-0.5 mol/1 NaOH and Na2C03) to solubilize a fraction of the OM. The basic extract is then acidified which causes a precipitate to form, i.e., humic acids (HA). The fraction, which remains in solution, is called fulvic acids (FA). Humin is the name given to the insoluble organic fraction that remains after extraction of humic and fulvic acids. At nearneutral pH (pH 5 - 8), which is characteristic of most natural water, the FA are the most water soluble of these three fractions. HA are somewhat less soluble, with their solubility increasing as the pH increases. Humin is insoluble at all pH values. 

The amphiphilic nature of dissolved humic substances (DHS) lends them the ability to associate with both hydrophobic organics and polar or ionic species [62-64]. Inorganic ions or mineral colloids in solution will interact with the electrically active surface of humic material in solution or in the solid phase according to the same bonding forces which lead to the association between SP0M and the solid mineral matrix. Humic matter in water is associated with... 

It has also been shown [254] that a commercial petroleum sulfonate surfactant which consists of a diverse admixture of monomers does not exhibit behavior typically associated with micelle formation (i.e., a sharp inflection of solvent properties as the concentration of surfactant reaches CMC). These surfactants exhibit gradual change in solvent behavior with added surfactant. This gradual solubility enhancement indicates that micelle formation is a gradual process instead of a single event (i. e., CMC does not exist as a unique point, rather it is a continuous function of molecular properties). This type of surfactant can represent humic material in water, and may indicate that DHS form molecular aggregates in solution, which comprise an important third phase in the aqueous environment. This phase can affect an increase in the apparent solubility of very hydrophobic chemicals. 

Formation constants for metals complexing with humic materials for marine and terrestrial sources. Source. From Millero, F., and D. Pierrot (2002). Chemistry of Marine Water and Sediment, Springer-Verlag, pp. 193-220. 

Experiments to identify disinfection by-products (DBFs) have been carried out using two different procedures. In the first, natural waters (e.g., river, lake) are reacted with the disinfectant, either in a pilot plant, an actual treatment plant, or in a controlled laboratory smdy. fii the second type of procedure, aquatic humic material is isolated and reacted with the disinfectant in purified water in a controlled laboratory study. This latter type of study is relevant because humic material is an important precursor of THMs and other DBFs. Aquatic humic material is present in nearly all natural waters, and isolated humic material reacts with disinfectants to produce most of the same DBFs found from natural waters. Because DBFs are typically formed at low levels (ng/L-pg/L), samples are usually concentrated to allow for DBF detection. Concentration methods that are commonly used include solid phase extraction (SFE), solid phase microextraction (SFME), liquid-liquid extraction, and XAD resin extraction (for larger quantities of water) [9]. 

Wershaw RL (1986) A new model for humic materials and their interactions with hydrophobic organic chemicals in soil-water or in sediment-water systems. J Contam Hydrol 1 29-45 Whitehouse BG (1984) The effect of temperature and salinity on the aqueous solubility of polynuclear aromatic hydrocarbons. Mar Chem 14 319-332 Wolters A, Linnemann V, Herbst M, Klein M, Schaffer A, Vereecken H (2003) Pesticide volatihzation from soil Lysimeter measurements versus predictions of European registration models. J Environ Qual 32 1183-1193... 

Mantoura R. C. F, Dickson A., and Riley J. P. (1978). The complexation of metals with humic materials in natural waters. Estuarine Coastal Mar. Set, 6 387-408. 

The solubility of fuel oil no. 2, particularly the alkane and isoprenoid fractions, in seawater is increased by the presence of fulvic acid, although the solubilities of phenanthrene or anthracene, both polycyclic aromatic hydrocarbons, are unaffected by the presence of humic materials (Boehm and Quinn 1973). Unfiltered Narragansett Bay water was able to dissolve 1,560 g/L of fuel oil no. 2, although removal of... 

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