Phosphorus features in FT-IR spectra of natural organic matter

Fourier-Transform Infrared （FT-IR） spectroscopy has been used extensively to characterize natural organic matter （NOM）. Absorption bands at 1100-1000 cm^-1 in the FT-IR spectra of NOM have been frequently assigned to alcoholic and polysaccharide C-O stretching or to vibrations of SiO2-related impurities. However, these interpretations do not consider that a strong band associated with P-O bonds of phosphate also appears in the same region. We evaluated the correlation between absorbance in this region and P content of 19 NOM samples from terrestrial, aquatic and plant shoot sources. In the spectra of 10 humic and fulvic acid samples, shoulder to minor bands appeared around 1050 cm^-1. Absorbance intensity at 1050 cm^-1 （Y） was linearly related to P content （X） by the following： Y=4.38X＋0.3 l, with R2=0.90. We did not observe such a close correlation between absorbance and P content in two aquatic NOM samples. Apparently, this is because the aquatic NOM samples were concentrated by reverse osmosis, which would have concentrated not only humic and fulvic acids but also other soluble organic solutes present in natural waters. In the FT-IR spectra of seven dissolved organic matter （DOM） samples obtained from dried plant shoots, broad and/or multiple bands around 1075 cm^-1 were observed with a shoulder at 977 cm^-1. These characteristics were more like those of organic phosphate compounds （such as inositol hexaphosphate）. However, solution 31P nuclear magnetic resonance spectroscopic analysis showed no significant amount of organic phosphate present in these samples.     

Forms and bioavailability of phosphorus associated with natural organic matter

Natural organic matter （NOM） is an important ingredient in soil which can improve physical, chemical, and biological properties of soils and nutrient supplies. In this study, we investigated the spectral features and potential availability of phosphorus （P） in the IHSS Elliott Soil humic acid standard （EHa）, Elliott soil fulvic acid standard Ⅱ （EFa）, Waskish peat humic acid reference （WHa）, and Waskish peat fulvic acid reference （WFa） by fluorescence spectroscopy, FT-IR, solution 31P NMR, 3-phytase incubation and UV irradiation. We observed more similar spectral features between EHa and EFa as well as between WHa and WFa than between the two humic acids or two fulvic acids themselves. Phosphorus in WHa and WFa was mainly present in the orthophosphate form. However, only about 5% was water soluble. After treatment by both UV irradiation and enzymatic hydrolysis, soluble orthophosphate increased to 17% of WHa P, and 10%o of WFa P. Thus, it appears that a large portion of P in Waskish peat humic substances was not labile for plant uptake. On the other hand, both orthophosphate and organic phosphate were present in EHa and EFa. Treatment by both UV irradiation and enzymatic hydrolysis increased soluble orthophosphate to 67% of EHa P and 52% of EFa P, indicating that more P in Elliott soil humic substances was potentially bioavailable. Our results demonstrated that source （soil vs. peat） was a more important factor than organic matter fraction （humic acid vs. fulvic acid） with respect to the forms and lability of P in these humic substances.     

Soil organic matter transport along an sub-Arctic river–sea transect

Bacteriohopanepolyols (BHPs) and glycerol dialkyl glycerol tetraethers (GDGTs) have potential as soil-tracing biomarkers for the extensive shelves of the Arctic Ocean. In this work these biomarkers were analysed in surface sediments along a well characterised sub-Arctic transect in the northernmost Baltic Sea from the Kalix River to the central Bothnian Bay to assess their environmental behaviour and potential for tracing the contribution of soil in this type of system. There was a high BHP diversity and enhanced total BHP concentration in the estuarine sediments, whereas a much less diverse pattern could be observed in the open bay with lower total BHP concentration. In addition, both soil marker BHPs (adenosylhopanes) and branched GDGTs were substantially more abundant in the estuarine than the open bay sediments.The $R_{\text{soil}}^{\prime }$ index, based on the R_soil index minus the contribution from the methylated soil marker BHPs, is suggested as a new approach for tracing soil derived organic matter (OM) in the (sub)-Arctic region. The index decreased along the transect in an off-river direction, correlating strongly with both the branched and isoprenoid tetraether (BIT) index and the stable carbon isotopic composition of the sedimentary organic carbon. These field results indicate that both the $R_{\text{soil}}^{\prime }$ and the BIT indices have potential for tracing soil derived OM in sub-Arctic to Arctic waters.     

Equilibrium sorption of phenanthrene and naphthalene on soil particulate organic matter

Soil organic matter (SOM) is the important phase for sorption of hydrophobic organic contaminants (HOCs) by soils and sediments. A linear partition model was invoked for mechanistically and quantitatively describing the sorption equilibria as partitioning…     

Isolation of natural organic matter from fresh waters using reverse osmosis and electrodialysis

This study was undertaken to solve the problem of removal of sulfate and silica from solutions of natural organic matter (NOM) that had been pre-concentrated by reverse osmosis. The goal is the development of a method by which NOM can be concentrated and …     

Can Rock-Eval pyrolysis assess the biogeochemical composition of organic matter during peatification?

Understanding the responses of soil organic carbon to an increase in global temperature is crucial to estimate potential feedbacks on global warming. In such a context, Rock-Eval pyrolysis has been recently proposed as a screening tool to investigate soil organic matter (SOM) chemistry and vulnerability. In order to test the validity of Rock-Eval as an indicator of SOM chemistry and of OM transformations, we compared classical Rock-Eval derived parameters (total organic carbon [TOC], Hydrogen Index [HI] and Oxygen Index [OI]) to Fourier infrared (FTIR) spectroscopy measured on peat sampled in two contrasting moisture conditions. The increase of TOC in the peat record depicted OM enrichment in aromatic moieties and lipids, whereas HI and OI, respectively, depicted the decomposition of carbohydrates and decarboxylation during early decay processes. Thought to be complementary to the classical parameters, other indicators based on the pyrolysis curve (S2) gave redundant or contradictory results. As an example, SOM cracking around 450 °C (namely the F3 component) was linked with carboxylic acids only in the dryer site. In the wetter one, no correlation was found between the F3 component and any FTIR absorption bands. This study underlined the current limitations of deconvolution derived parameters for the characterization of the biochemistry of OM. Finally, our work suggested that the routine use of Rock-Eval pyrolysis must be always associated with another characterization tool of OM, such as FTIR, to avoid misunderstanding.     

Determination of Hg and MeHg complexation with dissolved organic matter by fluorescence quenching titration

In natural waters inorganic mercury （Hg） and methylmercury （MeHg） are complexed with a variety of inorganic and organic ligands, such as OH^-, Cl^-, sulfide, thiols, and dissolved organic matter （DOM）. The bioavailability and toxicity of Hg and MeHg are related to their speciation, instead of their total concentrations. Among these species, Hg-DOM and MeHg-DOM complexes are the least known, due to the complexity and site-specificity of DOM in natural waters. Here we report the complexation between DOM and Hg or MeHg using fluorescence spectroscopy. The Suwannee River fulvic acid, peat humic acid, amino acid typotophan, and natural organic matter from the Suwannee River, Nordic River, and Delta Marsh were studied at their respective excitation/emission maxima,     

Optical characteristics and solar photodegradation of dissolved organic matter in Arkansas River, USA

Dissolved organic matter （DOM）, a mixture of numerous organic compounds of 30 to 300000 D, exists in all natural water resources including rivers, lakes and oceans, and plays a very important role in global carbon cycle and ecology. The DOM molecules absorb UV light strongly in short wavelengths and prevent microorganisms from being damaged by solar UV irradiation. Meanwhile, the large DOM molecules are then photodegraded into inorganic carbon and smaller organic molecules which are easier for bacterioplankton to digest. The Arkansas River is one of the largest rivers in the US, and a major input of organic materials to the Mississippi River and Gulf of Mexico. However, the photochemical properties of the DOM in the river water have not been investigated. To study this photodegradation process of the Arkansas River, water samples from the river were collected, filtered, sealed into quartz flasks, and exposed to sunlight for up to 15 hours. Some samples were retrieved from the flasks at certain time intervals. The intensity of the sunlight was measured during the exposure process at 30 min to 1 hr intervals. UV-vis absorption, fluorescence emission, 3D fluorescence spectra and DOM concentrations were determined for all retrieved samples. It was found that the total DOM concentration decreased while the dissolved inorganic carbon （DIC） concentration increased in the samples. UV absorption and fluorescence intensity of DOM decreased exponentially. The disappearance rate of UV absorption varied with wavelength. The loss of integral fluorescence was about 2.6 times that of the UV absorption at the excitation wavelength. In addition, the quantum yields also decreased, and the peak position of 3D fluorescence scan shifted to shorter wavelength.     

Bulk organic matter characteristics in the Pichavaram mangrove – estuarine complex,south-eastern India

The Pichavaram mangrove ecosystem is located between the Vellar and Coleroon Estuaries in south-eastern India. To document the spatial-depth-based variabilities in organic matter (OM) input and cycling, five sediment cores were collected. A comparative study was carried out of grain-size composition, pore water salinity, dissolved organic C (DOC), loss-on-ignition (LOI), elemental ratios (C/N and H/C), pigments (Chl a, Chl b, and total carotenoids), and humification indices. Sand is the major fraction in these cores ranging from 60% to 99% followed by silt and clay; cores from the estuarine margin have high sand content. In mangrove forests, pore-water DOC concentrations are high (32 ± 14 mg L⁻¹), whereas salinity levels are low (50 ± 5.5‰). Likewise, LOI, organic C and N, and pigment concentrations are high in mangroves. OM is mainly derived from upstream terrestrial matter and/or mangrove litter, and marine OM. The humification indices do not vary significantly with depth because of rapid OM turnover. The bulk parameters indicate that the Vellar and Coleroon Estuaries are more affected by anthropogenic processes than mangrove forests. Finally, greater variability and sometimes lack of specific trends in bulk parameters implies that the 2004 tsunami caused extensive mixing in sediments.     

Sedimentary environments of organic matter from Middle Permian source rocks in northern Xinjiang, China

1IntroductionThe formation of the Junggar,Turpan and Ili ba-sins is ascribed to Hercynian orogeny between theJunggar and Tianshan Mountains during the MiddlePermian.The rock assemblage of thick and stable sedi-mentary dark muddy shales interbedded with th…     

Mechanism of removing dissolved organic matter （DOM） by poly-silicic-ferric sulfate （PSF） coagulant

Chemical coagulation is very important in water treatment and was primarily designed for particle and turbidity removal. However, the concentration of dissolved organic matter （DOM） in drinking water and wastewater sources has increased greatly due to the development of industries and agricultures. Generally, the removal of DOM by conventional coagulation is not high, so enhanced coagulation has become a widely used method in developing or developed countries, in which a new type of efficient coagulant is developed as a cheap, practical and reasonable method. It has been widely recognized that the removal of DOM by iron-based coagulants is superior to that by aluminum salts. As a new type of inorganic polymer of iron-based salt, poly-silicic-ferric sulfate （PSF） has been studied since the late 20th century in Japan, but the mechanism of removing DOM still only concerns the essential recognition including adsorption/charge-neutralization, bridging, sweeping and so on. In this investigation, PSF was prepared by a particular co-polymerization method. The oxidization of PSF on humic acid （HA）, the hydrolysis law of PSF and the adsorption of HA on kaolin were studied. The characteristics [microstructure, size of species, Zeta potential and oxidation-reduction potential （ORP）] and coagulation performance of PSF were explored as compared to those of polyferric aluminum （PFA）. Mechanism of removing DOM （surrogated by humid acid （HA）） by PSF was analyzed primarily in terms of oxidization, hydrolysis species distribution, characteristics and coagulation behavior. The results showed that PSF is an oxidization coagulant and may change the molecular structure of HA, thus modifying the nature of HA surface and the nature of the interface between HA and water solution, and transforming the hydrophilic characteristics of HA into hydrophobic, thus improving the adsorption of HA. Different pH values give different influences on the complexation mode between HA oxidized by PSF, PSF and kaolin.     

Oxidant-elemental sulfur as an effective promoter for transformation of organic matter to hydrocarbons at moderate-low temperatures

Elemental sulfur is widely dispersed in the hydrocarbon source rocks and its depositional environment is usually thought as a reducing environment. The presence or absence of free oxygen is a key to identify oxidizing or reducing environment. But elemental sulfur is often present as an oxidant in this environment. When elemental sulfur meets with organic matter, redox reaction will occur. In our simulation experiments at 200 -400℃ , the existence of elemental sulfur can sharply increase the amounts of hydrocarbons, hence leading to the production of immature or low-mature oils and natural gases. At the temperature of 300℃ , the addition of elemental sulfur will further enhance the relative yields of hydrocarbons,and the final yield of total extracts and gaseous hydrocarbons of similitude kerogens by more than 463% and 2760% , respectively, while those of oil shales are increased by about 71% and 2044% , respectively. But at the temperature of 450℃, elemental sulfur plays a negative role in liquid hydrocarbon formation. The presence of elemental sulfur is probably a key factor in the gypsolyte environment leading to the formation of immature or low-mature oils, as well as the coexistence of immature or low-mature oils and natural gases.     

Characterization of organic matter deposited in the oriental zone from Moknine hypersaline environment, oriental Tunisia

The geochemistry data show that the total organic carbon （TOC） contents are high in the surface sediments in the eastern part of the Moknine＇ s Sebkha. Low decreasing of organic matter （ OM ） with increasing depth indicates the good preservation of OM in modern sediments. ＂Lignite levels＂ inserted in the sand sequence and deposited at the edge and in the intermediate zone are considered as lithologic and organic markers. It is characterized by high TOC and poor hydrogen index （HI） , indicating a higher plant origin and good preservation of OM in thin beds under anoxic condition. In all samples low values of HI are typical for strong terrigenous input in the Sebkha. Gas chromatography （GC） of saturate fraction showed that OM in the border zone is provided from plants but in the central zone OM is a mixture of terrestrial fraction and little fraction from microalgae. The study of free lipids indicated that this environment was influenced by intense bacterial and microbial activities, as evidenced by the abundance of n-alkanes and nC18-nC22.     

Origin and three-dimensional fluorescence spectrum of the chromophoric dissolved organic matter in Yangtze estuary, East China

Dissolved organic matter （DOM） is an important chemical component in natural water. Chromophoric dissolved organic matter （CDOM）, a fraction of optical properties, plays art important role in the biogeochemical cycle of nutrients in aquatic environment. People realized that DOM cycle is crucial in the global carbon and nitrogen flux, and also is inherently related to nutrients and trace metal elements. Therefore, CDOM was concerned by scientists in global oceanography and limnology fields. Water samples were collected from three sections （North Channel, South Channel and Zhuyuan） of the Yangtze （Changjiang River） estuary in March 2006 Three-dimensional excitation emission matrix （3-DEEM） fluorescence spectra were analyzed for those filtrates through Whatman GF/F filters. Dissolved organic carbon （DOC） was also measured by TOC analyzer. The tidal variety was also taken into account. The 3-D EEM fluorescence scans suggested the fluorescence characteristics of humic acid （Ex=332-344 nm, Em=439-451 nm） and fulvic acid （Ex=250-254 nm, Em=472-478 nm） were obvious, and the fluorescence group of protein-like and tyrosine （Ex=230 nm, Em=283 nm） was also found. They are mainly composed of CDOM in the Yangtze estuary. Further data analysis, especially the fluorescence index （f 450/500）, showed that terrestrial signal was rather strong （1.41-1.65） in the surface water, however, some terrestrial CDOM signals of bottom water showed excursions （1.28-1.39）. On the other hand, anthropogenic sign was impressed in the waters of Zhuyuan, which is one of the main drain outlets of Shanghai Metropolis. DOC concentrations ranged from 2.2 mg/L to 3.4 mg/L in Zhuyuan and South Channel, and from 2.0 mg/L to 2.4 mg/L in North Channel. The tide effect played a role in the composition of the CDOM measured by 3-D fluorescence scan technology.     

Submicron scale imaging of soil organic matter dynamics using NanoSIMS – From single particles to intact aggregates

The specific features of the nano-scale secondary ion mass spectrometry (NanoSIMS) technology with the simultaneous analysis of up to seven ion species with high mass and lateral resolution enables us to perform multi-element and stable isotope measurements at the submicron scale. To elucidate the power of this technique, we performed an incubation experiment with soil particles of the fine silt and clay fractions (from an Albic Luvisol), with occluded particulate organic material and intact soil aggregates (from a Haplic Chernozem), using a ¹³C and ¹⁵N labelled amino acid mixture as tracer. Before and during 6-day incubation after the addition of the label, samples were consecutively prepared for NanoSIMS analysis. For this purpose, two different sample preparation techniques were developed: (i) wet deposition and (ii) the sectioning of epoxy resin embedded samples. Single soil particles (fine silt/clay fraction) showed an enrichment of ¹³C and ¹⁵N after label addition that decreased over time. On aggregates of particulate organic matter, re-aggregated during the 6-day incubation experiment, we could show a spatially heterogeneous enrichment of ¹³C and ¹⁵N on the particle surface. The enrichment in ¹⁵N demonstrated the diffusion of dissolved organic matter into intact soil aggregate interiors. The prospects of NanoSIMS for three dimensional studies of stable C and N isotopes in organo-mineral associations is demonstrated by the recorded depth profiles of the organic matter distribution on mineral particles.     

Allochthonous versus autochthonous naturally occurring organic matter in the Anllóns river bed sediments (Spain)

Despite of the importance of the aquatic ecosystems as organic matter pools within the global carbon cycle, specific studies in river sediments are still insufficient. This study was carried out in an Atlantic basin where nine sites were selected in the lowest middle stretch of the River. The analyses include total organic carbon, C/N ratios, humus composition (humic, fulvic and humin), A2/A4 and A4/A6 ratios, biologically active organic matter (BAOM), water soluble organic matter (WSOC) and coloured water soluble organic carbon (CWSOC). The results suggested a predominance of allochthonous sources to the organic matter, highly influenced by the land uses together with the river hydrodynamics, namely urban and forest at sites 1, 2 and 9, and agricultural at sites 7 and 8. The 38% of the total organic matter was humic and fulvic acids. The biologically active organic matter, which may act as a proxy of microbial activity, showed a mean value of 0.9% of the total organic matter, showing the lowest values at sites with the highest organic matter total, soluble or coloured. This coloured organic matter represented an average of 3.60% of the total organic matter, and showed the highest visible light absorption at those sites more affected by human activities, close to centres of population (1, 2 and 9). This coloured fraction showed also a high degree of photostability. C/N ratios were less effective to discriminate between allochthonous or autochthonous sources, whereas A4/A6 ratios were effective to estimate variations of autochthonous sources, as it measures the variations of phytopigments of the river bed sediments.     

On genesis of organic matter in bottom sediments of hydrothermal field Ashadze-1, 13° N MAR

Comparative study of genesis and structure of dispersed organic matter (DOM) from background pelagic bottom sediments and sediments inside an active hydrothermal field Ashadze-1 collected during the cruise of the R/V “Professor Logachev” in 2003 was carried out. The received results allow to speak about an essential originality of structure and distribution of DOM in bottom sediments of the field Ashadze-1, according to unique physical and chemical conditions and facial specificity of sedimentation in hydrothermal zones. At the same time, attributes of petroleum hydrocarbons abiogenic synthesis hasn’t been fixed. Opposite, the received data allow to consider the process of fast maturing of biogenic OM in hydrothermal systems as a major factor of HC formation.     

Quantification and characterization of condensed organic matter in sediments from the Pearl River Delta and Estuary, South China

Nonhydrolyzable carbon （NHC） and black carbon （BC） were measured upon treatments with the HCl/HF/trifluoroacetic acid method, and with the combustion method at 375 ℃, respectively in three contaminated soils from the urban area of Guangzhou and twenty-two bulk and size-fractionated sediments from the Pearl River Delta and Estuary, China. The isolated NHC and BC fractions were also characterized using elementary analysis, radiocarbon accelerated mass spectroscopy （AMS）, solid state ^13C cross-polarization and magic angle spinning unclear magnetic resonance spectroscopy （^13C-CP/MAS NMR）, Fourier transformed infrared spectroscopy （FTIR）, and Raman microspectrometry. The results showed that the NHC and BC accounted for 25.6%-84.7 % and 4.14%-17.3%, respectively, of the total organic carbon （OC） with averages of 51.9% and 11.2% in the soils and sediments. For the less contaminated, low OC fiver and estuary sediments （WR and C08）, the OC and NHC concentrations increased with decreasing particle size.     

Molecular composition and indigenity of organic matter in Late Neoproterozoic sedimentary rocks from the Yangtze region, South China

1 Introduction As a linkage between the biosphere and the geosphere, organic geochemistry, especially molecular markers, has become a powerful tool for investigating important geological events and the evolutionary history of ancient life on Earth (Kvenvo…