Aquatic humic and fulvic materials

Characterization of Aquatic Humic and Fulvic Materials by Cylindrical Internal Reflectance Infrared Spectroscopy... 

Cylindrical internal reflectance infrared spectroscopy presents many advantages over conventional infrared techniques for the study of aquatic humic and fulvic materials. Samples can be studied in their natural state and in the aqueous environment from which they are isolated. Sample alterations due to drying and exposure to high pressures in the pellet forming process are avoided. In addition. 

I cability of fluorescence to the direct determination of functionality in humic substances is apparent from those reviews. Figure 14 (from Plechanov et al., 1983) shows the fluorescence spectra of several aquatic humic and fulvic acids. The relatively well-defined structure typical of the spectra of simple molecules such as anthracene (Fig. 15) is absent from the humic acid spectra. Ewald et al. (1983) report corrected fluorescence spectra for humic substances, but these spectra provide no further insight into the functionality of these materials. 

The classic definitions of soil humic and fulvic acids are based on solubility (Schnitzer and Khan, 1972). Thus, humic acid is the alkali-soluble material in soil, which is precipitated at pH 1. The material which remains soluble in the extract at pH 1 is fulvic acid. A more recent definition for aquatic humic substances is given by Thurman and Malcolm (1981). Here the material which adsorbs on an XAD column from an acid aqueous solution is defined as aquatic humus. That part of the adsorbed material which is soluble in acid and base is fulvic acid the portion insoluble in acid is humic acid. Another definition of an aquatic humic substance is based on adsorption by DEAE-cellulose columns (Miles etal., 1983). 

Aquatic humic substances may be found in groundwater, river water, lakes, marshes, bogs, swamps, and seawater. The source of the humates may be autochthonous or allochthonous that is, the humates may be formed from phytoplankton in the water or they may be leached into the aquatic environment from terrestrial plants, leaf litter, soil, or subsurface deposits. Relatively undisturbed marine environments have humic and fulvic acids formed almost entirely from native phytoplankton inland surface waters contain major contributions from allochthonous sources. Mixing of the two types of materials may occur, as in the estuaries of rivers. 

At present, soil derived humic matter and fulvic acids extracted from freshwater are available commercially and are commonly used to test techniques for DOM detection and also used as model compounds for trace metal chelation studies. The results obtained using these model compounds are frequently extrapolated to the natural environment and measurements on "real" samples provide evidence that this DOM is a good model compound. In the past, some investigators also made available organic matter isolated from marine environments using C18 resins. While these compounds come from aquatic sources, this isolation technique is chemically selective and isolates only a small percentage of oceanic DOM. Reference materials are not currently available for these compounds, which inhibits study of the role they play in a variety of oceanographic processes. 

NOM is common in sediments, soils, and near ambient (<50 °C) water. The materials result from the partial decomposition of organisms. They contain a wide variety of organic compounds, including carboxylic acids, carbohydrates, phenols, amino acids, and humic substances (Drever, 1997, 107-119 Wang and Mulligan, 2006, 202). Humic substances are especially important in interacting with arsenic. They result from the partial microbial decomposition of aquatic and terrestrial plants. The major components of humic substances are humin, humic acids, and fulvic acids. By definition, humin is insoluble in water. While fulvic acids are water-soluble under all pH conditions, humic acids are only soluble in water at pH >2 (Drever, 1997, 113-114). 

Sorption of humic substances from water on cation-exchange resins is extremely limited. MacCarthy and O Cinneide (1974) report that a cationic fraction of fulvic acid from a bog peat could be isolated with cation-exchange resin. However, aquatic humic material is strongly anionic, and sorption on cation-exchange resins is poor. 

Acidification of aqueous concentrates and extracts to pH near 1 is the standard procedure to precipitate humic from fulvic acid, and this procedure also has been applied to aquatic humic substances (Thurman and Malcolm, 1981). Aquatic humic substances that interact significantly with metal ions can be precipitated from water by addition of lead(Il) nitrate (Klocking and Mucke, 1969). Co-precipitation of aquatic humic materials with aluminum, copper, iron, and magnesium hydroxides has been used to recover aquatic humic substances from various types of water (Jeffrey and Hood, 1958 Williams and Zirino, 1964 Zeichmann, 1976). Humic acids can also be precipitated from an unconcentrated water sample by adding acetic acid and isoamyl alcohol to a sample contained in a separatory funnel, and after shaking, humic acid precipitates at the alcohol-water interface (Martin and Pierce, 1971). Precipitation methods are among the crudest of fractionation methods... 

Norwood D.L., Christman R.F. (1987), Structural characterisation of aquatic humic material. 2. Phenolic content and its relationship to chlorination mechanism in an isolated aquatic fulvic acid,... 

Humic materials have a wide range of molecular weights and sizes, ranging from a few hundred to as much as several hundred thousand atomic mass units. In general, fulvic acids are of lower molecular weight than humic acids, and soil-derived materials are larger than aquatic materials (7,2). Humic materials vary in composition depending on their source, location, and method of extraction however, their similarities are more... 

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