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.     

云南阳宗海表层沉积物有机质组成结构对磷赋存形态特征的影响

利用连续提取分级的方法定量分析阳宗海表层沉积物磷赋存形态,阐明了沉积物C、N、H和O组成及溶解有机质(DOM)紫外-可见光谱特征,探讨沉积物元素组成及DOM组成结构对不同形态磷含量的影响.结果表明:(1)沉积物潜在可移动磷含量在68.67~124.70 mg/kg之间变化,平均占总磷含量的9.81%,表现为BD-PNa OH-nr PNH_4Cl-P;沉积物稳定磷含量在496.73~908.28 mg/kg之间变化,平均占总磷含量的60.86%.(2)沉积物C、N含量和疏水性DOM光谱参数A_(240-400)表现出北部高、南部低的变化趋势,但H/C、O/C和(N+O)/C摩尔比和亲水性DOM光谱参数A_(240-400)变化趋势则与之恰好相反.(3)沉积物NH4Cl-P含量与C、N和H含量之间呈显著正相关,但与H/C、O/C、(N+O)/C摩尔比和亲水性DOM光谱参数E_2/E_3值之间呈显著负相关;NaOH-rP和BD-P+NaOH-rP含量均与O含量及O/H摩尔比呈显著负相关;NaOH-rP、BD-P+NaOH-rP和HCl-P均与疏水性DOM光谱参数A_(240-400)值之间呈显著正相关.因此,天然有机质元素组成及官能团结构是影响沉积物磷赋存形态的重要因素.     

Characterization of AOX by Fractionation Analysis and Size‐exclusion Chromatography

A characterization method for AOX in surface water samples was developed and tested. The method involves fractionation using a hydrophobic C18 resin and a weak anionic exchange resin and allows the fractionation of the AOX pool of surface water samples into four fractions: (1) hydrophilic acidic, (2) hydrophilic non‐acidic, (3) hydrophobic acidic, and (4) hydrophobic non‐acidic. The adsorption analysis was verified with AOX‐relevant model compounds and was applied to characterize the AOX pool of a stream sample from the Moskva river (Russia). In addition to the fractionation analysis, size‐exclusion chromatography was used to characterize the AOX pool of the sample studied. Hydrophilic acids made up the major fraction of the AOX pool (55 %). Among this fraction chlorinated high‐molecular acids (humic substances) made up the main fraction (35 %).     

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.     

Spectroscopic Investigation on Hydrophobic and Hydrophilic Fractions of Dissolved Organic Matter Extracted from Soils at Different Salinities

Organic matter can be considered one of the most important indicators of the extent of soil desertification processes. Among the causes of desertification, salinization induced by different factors is raising the greatest concern in the Mediterranean area. In the present research, hydrophilic (HI) and hydrophobic (HO) fractions of dissolved organic matter (DOM) extracted from soils at different degrees of salinization have been investigated by means of spectroscopic techniques such as tridimensional fluorescence spectroscopy in the mode of emission excitation matrix (EEM) and Fourier transform infrared spectroscopy (FT‐IR). The FT‐IR spectra were distinctive in differentiating HI from HO fractions and each DOM fraction as a function of soil salinity. The EEM spectra of HO fractions exhibited a shift toward longer emission wavelengths and higher fluorescence intensity (FI) values as compared to that of the HI fractions. These results could be ascribed to the different molecular complexities of HI and HO fractions. Further, a marked quenching effect was observed in the FI of both the DOM fractions with increasing soil salinity, which allowed to obtain immediate information on the soil salinity degree by comparing the fluorescence intensity.     

Variation in the photochemical lability of dissolved organic matter in a large boreal watershed

Boreal watersheds contain a vast quantity of terrestrially derived dissolved organic matter (DOM) originating from wetland and forest soils, yet variation in the potential for photochemical transformation of boreal aquatic DOM sources remains poorly understood. Laboratory solar radiation exposure experiments were conducted on DOM samples collected in three seasons, across nine sites, representing contrasting catchment composition and watershed position to assess variation in the photochemical lability of boreal DOM source and stable carbon isotopic signature (δ¹³C) of photomineralized DOM. Dissolved organic carbon (DOC) loss rates during laboratory exposure were lowest in summer, suggesting that DOM may have been more photo-degraded during summer. DOM from upstream portions of forested stream sites and wetland-influenced sites was more photolabile relative to downstream portions and the river DOM, suggesting potential losses in photolabile DOM downstream and in the lower reaches of the watershed. Increased a₂₅₄:a₃₅₀ and spectral slope following sample exposure suggest photoproduction of low molecular weight (LMW) CDOM and/or a higher photoreactivity of high molecular weight versus LMW compounds. Photomineralization of nitrogen was regulated by organic nitrogen concentration and resulted in NH₄ ⁺-photoproduction rates between 0.01 and 0.3?μM N?h^?1 and ecologically significant increases in NH₄ ⁺ for these waters. The δ¹³C of the photomineralized DOM was positively correlated to initial DOC concentration and generally lower when initial DOC concentrations were lower, suggesting variation in photomineralized DOM δ¹³C may be a result of kinetic isotope fractionation. Results from this study demonstrate significant variation in the photochemical lability of boreal watershed sources of DOM. Such variation suggests landscape and environmental change has the potential to alter the biogeochemical role photochemical transformations play in downstream portions of boreal watersheds.     

Spectrophotometric discrimination of river dissolved organic matter

There is a need to be able to differentiate the dissolved organic matter (DOM) fraction in river waters. Research in the 1970s and 1980s has attempted to utilize both absorbance and fluorescence to distinguish between DOM fractions in river waters, but both were limited by the available technology. Total organic carbon content has, therefore, been widely used as a standard method of measuring DOM concentration, although it has little power to differentiate DOM fractions. Recent advances in fluorescence spectrophotometry enable rapid and optically precise analysis of DOM. Here, we show how a combination of both fluorescence and absorbance can be used to discriminate statistically between spatial variations of DOM in tributaries in a small catchment of the Ouseburn, NE England. The results of the discriminant analysis suggest that about 70% of the samples can be correctly classified to its tributary. Discriminant function 1 explains 60·8% of the variance in the data and the fulvic‐like fluorescence intensity has the largest absolute correlation within this function; discriminant function 2 explains a further 21·5% of the variance and the fulvic‐like fluorescence emission wavelength has the largest absolute correlation within this function. The discriminant analysis does not correctly classify all tributaries every time, and successfully discriminates between the different tributaries 70% of the time. Occasions when the tributary waters are less well discriminated are due to either episodic pollution events (at two sites) or due to tributaries that have strong seasonal trends in spectrophotometric parameters, which allows the sites to be misclassified. Results suggest that spectrophotometric techniques have considerable potential in the discrimination of DOM in rivers. Copyright © 2002 John Wiley & Sons, Ltd.     

Effect of pH on binding of pyrene to hydrophobic fractions of dissolved organic matter(DOM) isolated from lake water

In order to better understand the compositional and structural complexity of dissolved organic matter(DOM) macromolecules and provide mechanistic information on the binding of hydrophobic organic contaminants(HOCs) to DOM, we fractionated large amounts of lake water into three hydrophobic DOM-fractions. The variation of the partitioning coef?cients(K_(DOC)) of pyrene at different p H levels was examined by ?orescence quenching titration. Results show that, relative to the more polar acidic DOM-fractions, the hydrophobic neutral fraction exhibits a higher sorption ability to pyrene. Generally, the sorption of pyrene to the three hydrophobic fractions is strongly pH-dependent. The K_(DOC) values of pyrene generally increase with decreasing p H levels, which is especially obvious in the sorption of pyrene to the fulvic acid fractions, suggesting that the binding is controlled by hydrophobic interactions. The mechanisms underlying the binding of pyrene to the hydrophobic fractions were also discussed. Our data are bene?cial to further understanding the binding of HOCs to DOM and how it has been affected,which may result in more accurate predictions of K_(DOC).     

Organic compounds in aerosol samples

In 1975, aerosols were collected with high-volume-samplers and impactors on the west coast of Ireland. The ether extractable organic material (EEOM) was separated into three main fractions: bases (B), acids (A), and neutral compounds (N). Each fraction is a very complex mixture of numerous species. Detailed investigations were carried out on these three main fractions. The individual species were determined quantitatively by gas chromatography. Qualitative identification was done by combined GC-MS.The concentration of total particulate matter (TPM) was in the range of 10 g/m³ (STP) air and the concentration of EEOM was 1 g/m³. The relative composition of the EEOM with regard to the main fractions A, B, and N was N>A>B — the same as in previous measurements. Particles with radii <1 m were investigated separately and showed an enrichment in organic matter.A comparison of individual species from several sample locations is now possible for then-paraffins C₁₀ to C₂₈. The concentrations of all thesen-paraffins are below 10 ng/m³, with no overall obvious preference for specific compounds and no obvious dependence on particle size above or below 1 m radius.A preliminary survey does not show any characteristic differences in the relative composition of the organic constituents of clean air aerosols from different sampling localities. The relative composition with regard to the three main fractions is rather uniform in clean air samples and in samples from polluted regions.     

Composition and sources of organic matter and its solvent extractable components in surface sediments of a bay under serious anthropogenic influences: Daya Bay, China

Organic matter of nine surface sediments from the Daya Bay was Soxhlet-extracted with a mixture of 2:1 (v/v) dichloromethane-methanol and separated into five fractions: non-aromatic hydrocarbons, aromatic hydrocarbons, ketones, alcohols, and fatty acids and asphaltenes, and analyzed to determine their bulk and biomarker composition. Marine autogenic input appears to be a major source of organic matter. Generally, non-aromatic hydrocarbons are the most dominant fraction of solvent-extractable organic matter (EOM) followed by the other four fractions in decreasing amounts: fatty acids and asphaltenes, ketones, alcohols and aromatic hydrocarbons. On average, both non-aromatic hydrocarbon fraction and fatty acid and asphaltene fraction account for approximately 40% of EOM. The sources of acyclic methyl ketones, alkanols and fatty acids were examined. For n-alkan-2-ones, allochthonous input is a more important source than marine autogenetic input; the reverse is true for n-fatty acids; for n-alkanols, allochthonous and autogenetic inputs seem comparable. Both n-alkan-2-ones and n-fatty acids in the surface sediments of different areas appear to be derived from common sources.     

Evaluation of the carbon isotopic effects of NDIR and CRDS analyzers on atmospheric CO2 measurements

Non-dispersive infrared(NDIR) and cavity ring-down spectroscopy(CRDS) CO_2 analyzers use 12CO_2 isotopologue absorption lines and are insensitive to all or part of other CO_2-related isotopologues. This may produce biases in CO_2 mole fraction measurements of a sample if its carbon isotopic composition deviates from that of the standard gases being used. To evaluate and compare the effects of carbon isotopic composition on NDIR and CRDS CO_2 analyzers, we prepared three test sample air cylinders with varying carbon isotopic abundances and calibrated them against five standard cylinders with ambient carbon isotopic composition using CRDS and NDIR systems. We found that the CO_2 mole fractions of the sample cylinders measured by G1301(CRDS) were in good agreement with those measured by Lo Flo(NDIR). The CO_2 values measured by both instruments were higher than that of a CO_2 isotope measured by G2201i(CRDS) analyzer for a test cylinder with depleted carbon isotopic composition δ~(13)C =-36.828‰, whereas no obvious difference was found for other two test cylinders with δ~(13)C=-8.630‰ and δ~(13)C=-15.380‰, respectively. According to the theoretical and experimental results, we concluded that the total CO_2 mole fractions of samples with depleted isotopic compositions can be corrected on the basis of their 12CO_2 values calibrated by standard gases using Lo Flo and G1301 if the δ~(13)C and δ18O values are known.     

Hydrologic and geochemical properties of the San Andreas fault at the Stone Canyon well

The Stone Canyon well penetrates 600 m of highly fractured and severely altered quartz diorite intimately associated with the creeping segment of the San Andreas fault of central California. Geophysical logs reveal a complex hydrology dominated by major fractures. Fluid pressure in some fractures is sufficient to prevent invasion of the formation by heavy drilling mud, implying pore pressures at least 10% higher than hydrostatic ones. At least three chemically distinct waters are encountered, including a chloride brine clearly segregated from the shallow, potable groundwater. Chemical alteration of the quartz diorite persists throughout the well, far below the depth where the water-rock reactions responsible for the ubiquitous chlorite and mixed-layer clays can be considered weathering. Whole-rock ¹⁸O analyses indicate significant interaction of the rocks with a low ¹⁸O fluid within some of the fractured and altered zones, whereas a deeper sample shows¹⁸O enrichment. High pore pressures encountered in Stone Canyon may be due to tectonic compression. Measurements of temporal variations in the pore pressure at the well may provide a means of predicting earthquakes along this segment of the San Andreas fault.     

River network travel time is correlated with dissolved organic matter composition in rivers of the contiguous United States

Most terrestrial allochthonous organic matter enters river networks through headwater streams during high flow events. In headwaters, allochthonous inputs are substantial and variable, but become less important in streams and rivers with larger watersheds. As allochthonous dissolved organic matter (DOM) moves downstream, the proportion of less aromatic organic matter with autochthonous characteristics increases. How environmental factors converge to control this transformation of DOM at a continental scale is less certain. We hypothesized that the amount of time water has spent travelling through surface waters of inland systems (streams, rivers, lakes, and reservoirs) is correlated to DOM composition. To test this hypothesis, we used established river network scaling relationships to predict relative river network flow-weighted travel time (FWTT) of water for 60 stream and river sites across the contiguous United States (3090 discrete samples over 10 water years). We estimated lentic contribution to travel times with upstream in-network lake and reservoir volume. DOM composition was quantified using ultraviolet and visible absorption and fluorescence spectroscopy. A combination of FWTT and lake and reservoir volume was the best overall predictor of DOM composition among models that also incorporated discharge, specific discharge, watershed area, and upstream channel length. DOM spectral slope ratio (R² = 0.77) and Freshness Index (R² = 0.78) increased and specific ultraviolet absorbance at 254 nm (R² = 0.68) and Humification Index (R² = 0.44) decreased across sites as a function of FWTT and upstream lake volume. This indicates autochthonous-like DOM becomes continually more dominant in waters with greater FWTT. We assert that river FWTT can be used as a metric of the continuum of DOM composition from headwaters to rivers. The nature of the changes to DOM composition detected suggest this continuum is driven by a combination of photo-oxidation, biological processes, hydrologically varying terrestrial subsidies, and aged groundwater inputs.