Organically Bound Nutrients in Dissolved Organic Matter Fractions in Seepage and Pore Water of Weakly Developed Forest Soils

Previous field and laboratory studies showed that organically bound nutrients can contribute largely to the export of N, P, and S from soil into aquatic systems. One possible determinant for the losses of dissolved organic nutrients leaving the soil environment could be their distribution between dissolved organic matter (DOM) fractions of different mobility in soil. To elucidate the potential influence of DOM fractions under varying flow conditions on the vertical translocation of organically bound nutrients, we determined the concentrations and fluxes of dissolved organic C (DOC) and nutrients (DON, DOP, DOS) in soil water under a Scots pine (Pinus sylvestris L.) and a European beech (Fagus sylvatica L.) forest. We sampled seepage water from the organic forest floor layer and the mineral subsoil using zero‐tension lysimeters and soil pore water using tension lysimeters and suction cups. DOM in soil water was fractionated into hydrophilic and hydrophobic compounds by XAD‐8 at pH 2. We found that the organic forest floor layers were large sources for DOC, DON, DOP, and DOS. The dissolved organic nutrients were mainly concentrated in the hydrophilic DOM fraction which proved to be more mobile in mineral soil pore water than the hydrophobic one. Consequently, the concentrations and fluxes of dissolved organic nutrients decreased less with depth than those of DOC. Concentrations as well as fluxes in subsoil pore water of DOC and dissolved organic nutrients in the studied weakly developed soils were high as compared with literature data on deeply developed forest soils. Under conditions of rapid water flow through the strongly structured mineral soil at the beech site, almost no retention of DOM took place and thus the influence of the distribution of organically bound nutrients between the DOM fractions on the export of DON, DOP, and DOS was negligible.     

Dissolved Organic Carbon Fractions Formed during Composting of Municipal Solid Waste: Properties and Significance

The properties and transformation of dissolved organic matter (DOM) extracted (10 L water per kilogram compost) from municipal solid waste (MSW) compost at five stages (days 47, 77, 105, 126, and 187) of composting were investigated. The DOM was fractionated into hydrophobic or hydrophilic neutrals, acids, and bases. The unfractionated DOM, the hydrophobic acids and neutrals (HoA and HoN, respectively), and the hydrophilic neutrals (HiN) fractions were studied using solid-state ¹³C-NMR, FTIR, and DRIFT spectroscopy. The HoA fraction was found to be the dominant (percentage of total DOM) hydrophobic fraction, exhibiting a moderate increase during composting. The HoN fraction increased sharply from less than 1% to 18% of the total DOM during 187 days of composting, while the hydrophobic bases (HoB) exhibited the opposite trend. The HiN represented the major fraction of the hydrophiles up to 120 days of composting, decreasing thereafter by 38%. The relative concentration of the hydrophilic acids and bases (HiA and HiB, respectively) exhibited no consistent trend during composting. DRIFT spectra of the unfractionated DOM taken from the composting MSW revealed a decreasing level of polysaccharide structures with time. The ¹³C-NMR and FTIR spectra of the HoA fraction exhibited a polyphenol-humic structure, whereas the HoN spectra exhibited strong aliphatic features. The spectra of the HiN fraction confirmed its polysaccharide nature. During the final stage of composting, the DOM concentration was steady, while a relative decrease of HiN concomitant with an increase of HoA and HoN fractions was observed. These indicate that the DOM contained a low concentration of biodegradable organic matter and a higher content of macromolecules related to humic substances. The biological significance and heavy metal binding of these fractions are being studied based on earlier observations showing enhanced plant growth in the presence of DOM extracted from mature as opposed to immature compost.     

Metal Distribution in Different Size Fractions of Natural Organic Matter

In this paper, size‐exclusion chromatography (SEC) was used to determine the metal concentration in different size fractions of a bog lake water. Two methods were applied: (a) preparative SEC with off‐line metal concentration analysis and (b) direct coupling of an analytical SEC system on‐line with an inductively‐coupled plasma mass spectrometer (ICP‐MS). In the preparative SEC measurements, maximum concentrations were found for different metal ions in different size fractions of the natural organic matter (NOM). Normalization of metal concentrations to dissolved organic carbon concentration (DOC) yielded two maxima in the high and in the very low molecular‐weight fractions. Whereas good recoveries were found for Al, Fe, and Ni, only 40% were obtained for Pb. This indicates that Pb formed labile complexes with NOM, and hence could strongly interact with the column material. In the experiments with the analytical SEC‐ICP‐MS system, the same trends were observed, but with even lower recoveries than in the preparative system. Sample preconcentration and storage were also investigated with respect to decrease in metal concentration. During the ultrafiltration preconcentration step Al and Fe were removed only to a small extent, whereas about half of the initial Pb was lost. This indicates that Al and Fe were mainly bound to high molecular‐weight fractions of NOM. In contrast to that, Al and in particular Fe were removed from solution more than proportionally with respect to DOC because of aggregation of the NOM during storage, whereas Pb and Ni were concentrated relative to the DOC.     

Total Organic Carbon (TOC) as a Sum Parameter of Water Pollution in Selected Polish Rivers (Vistula,Odra, and Warta)

This paper reports on total organic carbon (TOC) and its fractions dissolved organic carbon (DOC) and particulate organic carbon (POC) studied in different Polish rivers. The samples investigated came from the Vistula, Odra, and Warta rivers, and were compared with similar data on river waters available in the literature. The DOC concentrations ranged from 10.0 to 14.2 mg/L and did not vary during the vegetative season. The POC values considerably increased from May through September and reached a maximum in summer. Results for the years 1991τ1996 evidenced a significant increase in the POC value for the Polish rivers from 10.8 to 24.5 mg/L, in comparison with analogous values for West European rivers and North American ones. The enhanced values of TOC and POC were interpreted as being due to anthropogenic pollution.     

A Preliminary Study of Chromophoric Dissolved Organic Matter (CDOM) in Lake Taihu,a Shallow Subtropical Lake in China

The optical properties and spatial distribution of chromophoric dissolved organic matter (CDOM) in Meiliang Bay of Lake Taihu were evaluated and compared to the results in literature. Concentrations of dissolved organic carbon (DOC) ranged from 8.75 to 20.19 mg L^?1 with an average of (13.10 ± 3.51) mg L^?1. CDOM absorption coefficients a(λ) at 280 nm, 355 nm, and 440 nm were in the range 11.28...33.46 m^?1 (average (20.95 ± 5.52) m^?1), 2.42...7.90 m^?1 (average (4.92 ± 1.29) m^?1), and 0.65...2.44 m^?1 (average (1.46 ± 0.44) m^?1), respectively. In general, CDOM absorption coefficient and DOC concentration were found to decrease away from the river inflow to Meiliang Bay towards the lake center. The values of the DOC‐specific absorption coefficients a*(λ), given as absorption coefficient related to mass concentration of organic carbon (C) ranged from 0.28 to 0.47 L mg^?1 m^?1 at 355 nm. The determination coefficients between CDOM absorption and DOC concentration decreased with the increase of wavelength from 280 to 550 nm. The linear regression relationship between CDOM absorption at 280 nm and DOC concentration was following: a(280 nm) = 1.507 L mg^?1 m^?1 · DOC + 1.215 m^?1. The spectral slope S values were dependent on the wavelength range used in the regression. The estimated S values decreased with increasing wavelength range used. A significant negative linear relationship was found between CDOM absorption coefficients, DOC‐specific absorption coefficients and estimated S values especially in longer wavelength range. The linear regression relationship between DOC‐specific absorption coefficients at 440 nm and estimated S values during the wavelength range from 280 to 500 nm was following: a*(440 nm) = (–0.021 μm · S + 0.424) L mg^?1 m^?1.     

Mobilisierbarkeit von hydrophoben organischen Schadstoffen in belasteten Böden und Abfällen. Teil II: Mobilisierbarkeit von PAK,PCB und Phenolen durch reale Wässer

Mobilization Potential of Hydrophobic Organic Compounds (HOCs) in Contaminated Soils and Waste Materials. Part II: Mobilization Potential of PAHs, PCBs, and Phenols by Natural Waters To evaluate the hazard potential of organic pollutants in a soil, the mobilization potential of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and phenol derivatives in different waters was ascertained by elution experiments and compared to common elution procedures. Furthermore, dissolved organic matter from different sources was examined with regard to its influence on solubility. The results of the elutions pointed out that depending on the composition of the water sample, the leaching behaviour of the PAHs and PCBs is very different and is determined not only by the concentration of the dissolved organic carbon (DOC) but particularly by its quality. The separation of DOC-associated and “free” dissolved pollutants with the solid-phase extraction on C18-reversed phases revealed the responsibility of the sorption of the pollutants to the DOC for their solubility and mobilization. Moreover, an increase of association of pollutants to the DOC was observed with growing hydrophobicity corresponding to their octanol/water partition coefficient K_ow. The comparison of the elutions showed that the exclusively used S4-elution (German standard DIN 38414 part 4) is not appropriate to evaluate the mobilization of hydrophobic organic pollutants realistically. The eluted PAHs (PCBs) of the S4-elution were exceeded in landfill leachate by a factor of 7 (7), in the pond water by a factor of 9 (15), and in the compost saturation extract even by a factor of 35 (56). In contrast, a realistic “worst-case” leaching could be simulated with a tensidic SDS-solution corresponding to an elution process evaluating the mobilization of organic pollutants. The DOC of real waters and surfactants has little influence on the mobilization of the comparatively polar phenols. Concerning a “worst-case” evaluation of mobilization, the S4-elution under alkaline conditions is doubtlessly useful for water-soluble phenols.     

Characterization of industrial wastewaters using gel-permeation chromatography with multicomponent detection

The gel-permeation chromatography system with multicomponent detection of organic carbon, organic nitrogen, organic halogen, and UV/vis absorption measurement is shown to be a useful tool for characterization of industrial wastewaters and wastewater treatment processes. The proposed system was used to investigate biologically treated wastewater from chemical industry, whereby one branch stream was identified to be the main source of persistent halogenated organics. Various treatment processes of pulp mill wastewater were also evaluated revealing that precipitation with aluminium is very effective for the removal of the high molecular fraction whereas the biological treatment is generally less selective. In the biological treatment of tannery wastewaters, it has been shown that the aerobic treatment, in contrast to anaerobic step, causes evident alterations of the composition of the polar DOC fraction. The nitrogen containing compounds are also better decomposed in the aerobic step compared to the anaerobic one.     

Molar Masses and Radii of Humic Substances Measured by Light Scattering

A bulk aquatic natural organic material (NOM) was characterized by high-performance size exclusion chromatography (HPSEC) coupled with multi-angle laser light scattering (MALLS), UV-Vis, and refractive index detection. This technique was used to measure the molar mass and radius of the natural organic matter in solution. Results indicate that the NOM aggregates to a large extent at the concentrations used in this study (5... 15 mg mL^–1). The solution conditions of pH and ionic strength were also shown to affect the measured size of NOM. The number and type of HPSEC columns also influenced these measurements. The importance of using multiple detectors was illustrated by peaks that were not detected by all the detectors. While these data are preliminary and have large errors associated with them, it is nevertheless an indication that HPSEC-MALLS can be used to investigate the effects of solution conditions and aggregation on the size of humic substances in solution.     

Alkaline Degradation of Dissolved Organic Matter

The degradation of dissolved organic matter (DOM) was studied in alkaline solution. The products were characterised using UV/vis spectroscopy, size‐exclusion chromatography (SEC), and by the analysis of low‐molecular‐weight organic acids (LMWOA). The degradation experiments were performed with water from a brown water lake or its isolated fulvic acid fraction and sodium hydroxide at different reaction times and temperatures. Depending on the wavelength and the reaction time, the UV/vis absorbance between 230 nm and 600 nm increased or decreased. The behaviour of model compounds during reactions in alkaline media was compared to the UV/vis spectroscopic behaviour of DOM. The release of LMWOA was described by kinetic data and compared to the data of model reactions. Evidence was given for the carboxylic esters playing a significant role in the release of LMWOA only during the beginning of the alkaline degradation. The results gained by SEC with on‐line UV and DOC detection showed that the average size of DOM was decreasing, and that a major part of the degradation products consisted of low‐molecular‐weight mono‐ and dicarboxylic acids.     

Dissolved Organic Carbon in Seepage Water – Production and Transformation during Soil Passage

Dissolved organic carbon (DOC) in seepage water can combine with organic pollutants, with Al and heavy metal ions and transport them through the soil profile with a potential to contaminate groundwater. We studied the production of DOC in aerobic decomposition experiments at 8 °C and moisture close to field capacity in soils from two sites with different microbial activities (spodic dystric Cambisols with moder (SLB) and mor‐moder (SLS) layers) using ¹³C‐depleted plants of differing decomposability (Epilobium angustifolium and Calamagrostis epigeios). Additionally, we investigated the DOC transformation during soil passage in decomposition experiments and in the field for the sites SLB and SLS. For SLS, decomposition of Epilobium resulted in a cumulative CO₂ production of 14% of the added C within 128 days. Priming effects were negligible. CO₂ production for the experiments using Calamagrostis was less with 11% for SLB and 10% for SLS. Cumulative DOC production was markedly high in the Epilobium decomposition experiment, being 25 g m^–2, out of which 11 g m^–2 were Epilobium‐derived (2% of the added C). For the Calamagrostis experiments, cumulative productions of DOC and Calamagrostis‐derived DOC (0.1% of the added C for SLS and SLB) were much less. During the soil passage, much of the DOC was removed by sorption or decomposition processes. Field studies at SLS and SLB using ¹³C natural abundance showed that ¹³C distribution of soil organic matter increased with depth, probably mainly due to a discrimination of C isotopes by decomposing microorganisms. DOC, however, showed a depletion of ¹³C from –28γ PDB to –29γ (SLB at 40 cm) or –28 to –30γ (SLS at 20 cm) with depth, owing to preferential decomposition of ¹³C‐enriched substances or preferential adsorption. This study indicates that DOC production is strongly affected by litter composition and that significant changes in DOC composition may occur during its passage through a soil depth of 40 cm.     

On the use of UV spectrophotometry to assess dissolved organic carbon origin variations in the Upper Rhône River

To detect temporal changes and the origin of the refractory dissolved organic matter in the Upper Rhône River, UV light absorbance (A) at 285 nm and quantitative dissolved organic carbon (DOC) measurements were carried out. Data from 63 visits to the main channel over a period of two years and from visits to different waterbodies in the alluvial plain before and after a flood are presented. There was a good correlation between A (0.019–0.160) and the DOC content (1.40–9.81 mg/L) for the waterbodies, but not for the river axis with lower A (0.013–0.044) and DOC content (1.13–2.20 mg/L). Due to this good correlation, the DOC content could be quantified for the waterbodies by absorbance measurements only. For the river water this indirect determination of the DOC content was not possible. However, the A/DOC ratio showed changes in the composition of DOC of river water and provided indications about the origin of the dissolved organic matter in the Upper Rhône River.     

Adsorbed and Bound Residues in Fulvic Acid Fractions of a Contaminated Groundwater – Isolation:, Chromatographic and Spectroscopic Characterization

Humic substances (HS) were isolated from two contaminated groundwater samples (B22 and B53) from a site of a former gas facility. The isolation yielded almost only the fulvic acid fractions (FA). For characterization spectroscopic (UV, fluorescence) and chromatographic techniques (hydrophobic interaction chromatography – HIC as well as size-exclusion chromatography – SEC) were applied. The sample designated B22 FA was collected from the contamination plume whereas the sample B53 FA was collected downstream. Distinct differences were exhibited by these samples. The UV and fluorescence spectra as well as the HIC and SEC chromatograms of the B53 FA sample resemble those of the FA fraction obtained from natural water (groundwater, bog). The HIC and SEC chromatograms reveal the presence of organic compounds in B22 FA which can be derived from coal tar contaminants or their metabolites. Some of the compounds can be extracted from the FA fraction with non-polar organic solvents indicating adsorptive forces between the contaminants and the FA fraction.     

Seasonal changes in iron transport and nature of dissolved organic matter in a humic river in northern Finland

Changes in the concentration of iron and dissolved organic matter (DOM), and in the colour and fluorescence properties in the River Kiiminkijoki were investigated as functions of the seasonal flow regime over a two-year period. The iron concentration in filtrates and the ratio of Fe to DOC in the river increased under low flow conditions and decreased during the flood periods. The colour of the dissolved organic matter increased with increasing iron content, the effect being more pronounced during the warm period of the year than in winter. The ratio of fluorescence to DOC increased during the warm period of the year but not in winter, and decreased rapidly with discharge at the beginning of the flood period in autumn. The results give indications of the origin, formation, nature, and fate of the DOM in the river water. Temperature-dependent microbiological processes in the formation and sedimentation of iron-organic colloids seem to be important. Estimates are given for the amounts and transport rates of iron discharged into the Gulf of Bothnia by the river.     

Determination of dissolved organic matter in streamwater using visible spectrophotometry

Absorbance at 360 nm was measured on 44 filtered streamwater samples of different dissolved organic matter (DOM) contents. A regression equation of DOM on absorbance predicted DOM with a standard error of estimate of 1.26 mgl^?1, Use of a published equation relating dissolved organic carbon (DOC) to absorbance gave DOC values for the samples which were consistent with measured DOM. The method offers considerable potential for rapid quantification of dissolved organic matter concentrations in streamwater.     

Characterization of Estuarine and Fluvial Dissolved Organic Matter by Thermochemolysis using Tetramethylammonium Hydroxide

Selected samples of dissolved organic matter (DOM) isolated by ultrafiltration (UDOM) have been analyzed by thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH). This technique cleaves ester and ether bonds of bio‐ and geological macromolecules and releases monomer subunits and methylates them in situ as their methyl ethers and methyl esters. Compared with conventional pyrolysis, TMAH thermochemolysis avoids decarboxylation of preexisting carboxylic moieties and produces aromatic acids as their methyl esters. Various phenolic derivatives, which might originate from incorporated lignin‐derived structures, from the highly aliphatic and resistant biopolymer cutan and also from proteinaceous materials, were identified among the products produced from UDOM upon thermochemolysis. The presence of lignin derivatives in UDOM indicates input of organic matter derived from terrestrial sources. Various aromatic acids, perhaps representing the final steps in the oxidation of the side‐chain during microbial oxidation of lignin, were released upon TMAH thermochemolysis, suggesting they are structural constituents of the UDOM. Different ratios of lignin‐derived materials, commonly determined using the CuO oxidation method, such as the Δ value, indicative of the amount of lignin present, the acid/aldehyde ratio (Ad/Al)_G, indicative of the extent of oxidative degradation of the lignin component, and the syringyl/guaiacyl (S/G) and p‐hydroxyphenyl/guaiacyl (P/G) ratios, indicative of the contribution for the different types of lignin, were determined.     

Degradation and Leaching of Napropamide in BRIS Soil Amended with Chicken Dung and Palm Oil Mill Effluent

The degradation and leaching of napropamide were compared between Beach Ridges Interspersed with Swales (BRIS) soil samples, and the same soil samples amended with 20 mg ha^?1 of either chicken dung (CD) or palm oil mill effluent (POME). The effects of removing dissolved organic carbon (DOC) from the soil samples on napropamide degradation and leaching were also studied. The addition of CD and POME to BRIS soil increased the napropamide half‐life values to 69 and 49.5 days, respectively. Sterilization of the soil samples resulted in partial inhibition of napropamide degradation in all soil samples. The half‐lives of napropamide in BRIS soils receiving 0, 20, 100, and 200 mg kg^?1 of DOC derived from CD were 43, 46.2, 53.4, and 63 days, respectively. The napropamide half‐lives in soil samples treated with 0, 20, 100, and 200 mg kg^?1 of DOC derived from POME were 43, 49.2, 57.7, and 69 days, respectively. However, in the sterilized soil samples, there were no significant effects of adding DOC derived from either CD or POME on napropamide half‐lives. Incorporating either CD or POME decreased napropamide leaching and total amounts of napropamide remained in the soil columns after two pore volumes of water has been leached were higher in the amended than the non‐amended soil. The CD was more effective in decreasing napropamide leaching than the POME. There were no effects of DOC on napropamide leaching in all soil treatments.     

Dissolved Carbohydrate Concentration,Composition, and Bioavailability to Microbial Heterotrophs in Stream Water

Dissolved total carbohydrates (DTCH), dissolved free monosaccharides (DFMS), dissolved organic carbon (DOC), biodegradable DOC (BDOC), and humic substances (HS) were measured in White Clay Creek (WCC), a stream in southeastern Pennsylvania Piedmont, USA. Samples were collected over different seasons and under baseflow and stormflow conditions. DOC concentrations ranged from 1.0 to 12.8 mg/L C with the highest concentrations associated with stormflows. Carbohydrates ranged from 0.42 to 12.4 μM and accounted for 2.9 to 12.7% of the DOC. Humic substances represented the major DOC fraction, accounting for 55 to 72% of the DOC pool under all flow conditions. The humic fraction had a lower carbohydrate content (4.4%) than the non-humic fraction of DOC (7.2%). Stormflow DOC was enriched in carbohydrates relative to baseflow DOC, but the percentage of humic-C changed little. Carbohydrates were primarily present as dissolved polysaccharides (55%), but a significant fraction was bound to humic substances (40%), while a small proportion was present as monosaccharides (5%). The major monosaccharides in stream water, listed in order of decreasing concentration, included glucose, galactose, rhamnose, xylose, arabinose, mannose, and fucose. On average (30.6 ± 7.4)% (n = 44) of the stream water DOC was biodegradable, and carbohydrates accounted for 9.9 to 17.7% of the BDOC.     

Approaches to the Immunochemical Analysis of Non-extractable Triazine Residues in Refractory Organic Substances (ROS) and Characterization of ROS

The tendency of several pesticides to form non-extractable residues requires simple and fast screening methods. Immunochemical methods can meet this demand. They are based on selective and highly sensitive antibody binding to pesticide residues exposed on refractory organic substances (ROS). s-Triazines were used as an example to show the feasibility of this approach. It was proven that under laboratory conditions atrazine was bound to ROS. Antibody recognition pointed to the availability of free ethyl and isopropyl groups exposed at the non-extractable s-triazine residue. Therefore, it is suggested on the basis of antibody selectivities that binding of atrazine to ROS may take place by substitution of the chlorine residue. In the next step, aquatic ROS isolated from surface waters located in an agricultural area were examined for non-extractable s-triazines. ROS from a lake were found to contain bound residues, whereas none were detected in the creek samples. As an outlook the feasibility of serological characterization of ROS is discussed. The novel concept of serotyping is based on the fractionation of ROS by electrophoretic techniques followed by an immunoreaction with polyclonal antibodies directed against different ROS. When immunoelectrophoresis is used, precipitation lines can be compared and checked for identity and cross-reactivity. This approach can form the basis for classifying ROS and determine similarities with unknown ROS.     

Time-resolved Fluorescence Measurements of Aquatic Natural Organic Matter (NOM)

The fluorescence decay of aquatic natural organic matter (NOM) samples was investigated using the time-correlated single photon counting technique (TCSPC). Two different approaches for the data analysis are presented: the discrete component approach (DCA) and the exponential series method (ESM). The parameter set obtained in the DCA is discussed in terms of characterization for NOM of different origins. However, the obtained parameter set can only be interpreted as operationally defined. Using the ESM for a fluorescence decay time distribution analysis no a priori assumption about the number of fluorescing components was introduced into the data analysis. The interpretation of fluorescence decay time data for samples before and after ozonation is in good agreement with results of other analytical methods.