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Natural Organic Matter (natural + organic_matter)
Selected AbstractsTRACE METAL UPTAKE, NATURAL ORGANIC MATTER, AND THE FREE-ION MODELJOURNAL OF PHYCOLOGY, Issue 1 2005Robert J. M. Hudson First page of article [source] Copper toxicity in relation to surface water-dissolved organic matter: Biological effects to Daphnia magnaENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 12 2004Kees J.M. Kramer Abstract Water quality standards for copper are usually stated in total element concentrations. It is known, however, that a major part of the copper can be bound in complexes that are biologically not available. Natural organic matter, such as humic and fulvic acids, are strong complexing agents that may affect the bioavailable copper (Cu2+) concentration. The aim of this study was to quantify the relation between the concentration of dissolved natural organic matter and free Cu2+ in surface waters, and the biological effect, as measured in a standardized ecotoxicological test (48 h-median effective concentration [EC50] Daphnia magna, mobility). Six typical Dutch surface waters and an artificial water, ranging from 0.1 to 22 mg/L dissolved organic carbon (DOC), were collected and analyzed quarterly. Chemical speciation modeling was used as supporting evidence to assess bioavailability. The results show clear evidence of a linear relation between the concentration of dissolved organic carbon (in milligrams DOC/L) and the ecotoxicological effect (as effect concentration, EC50, expressed as micrograms Cu/L): 48-h EC50 (Daphnia, mobility) = 17.2 × DOC + 30.2 (r2 = 0.80, n = 22). Except for a brook with atypical water quality characteristics, no differences were observed among water type or season. When ultraviolet (UV)-absorption (380 nm) was used to characterize the dissolved organic carbon, a linear correlation was found as well. The importance of the free copper concentration was demonstrated by speciation calculations: In humic-rich waters the free Cu2+ concentration was estimated at ,10,11 M, whereas in medium to low dissolved organic carbon waters the [Cu2+] was ,10,10 M. Speciation calculations performed for copper concentrations at the effective concentration level (where the biological effect is considered the same) resulted in very similar free copper concentrations (,10,8 M Cu) in these surface waters with different characteristics. These observations consistently show that the presence of organic matter decreases the bioavailability, uptake, and ecotoxicity of copper in the aquatic environment. It demonstrates that the DOC content must be included in site-specific environmental risk assessment for trace metals (at least for copper). It is the quantification of the effects described that allows policy makers to review the criteria for copper in surface waters. [source] Attenuating effects of natural organic matter on microcystin toxicity in zebra fish (Danio rerio) embryos,benefits and costs of microcystin detoxicationENVIRONMENTAL TOXICOLOGY, Issue 1 2006Jimena Cazenave Abstract To contribute to the understanding of joined factors in the environment, impact of pure microcystins (-RR and -LF) on zebra fish (Danio rerio) embryos were investigated individually and in combination with a natural organic matter (NOM). The applied NOM was a reverse osmosis isolate from Lake Schwarzer See (i.e., Black Lake, BL-NOM). Teratogenic effects were evaluated through changes in embryonic development within 48 h of exposure. Detoxication activities were assessed by the activities of phase II biotransformation enzymes, soluble and microsomal glutathione S -transferase (s, mGST). Oxidative stress was assessed by determining both the production of hydrogen peroxide and by analyzing the activities of the antioxidative enzymes, guajacol peroxidase (POD), catalase (CAT), glutathione peroxidase (GPx), and the glutathione restoring enzyme glutathione reductase (GR). Energetic costs were evaluated by determining contents of fat, carbohydrates, and proteins in both exposed and control embryos. BL-NOM attenuated toxic effects of MC-LF and MC-RR verified by less pronounced teratological effects within 24 h, in particular, as well as less rise in the activity of s-GST, when compared with embryos exposed to either pure toxins or in combination with organic matter. BL-NOM also diminished oxidative effects caused by MC-LF; however, it failed to attenuate oxidative stress caused by MC-RR. Content of lipids was significantly reduced in exposed embryos following a trend similar to that obtained with teratological and enzymatic assays confirming the attenuating effect of BL-NOM. Physiological responses to microcystins and NOM required energetic costs, which were compensated to the expense of the energy resources of the yolk, which in turn might affect the normal development of embryos. © 2006 Wiley Periodicals, Inc. Environ Toxicol 21: 22,32, 2006. [source] Binding of ciprofloxacin by humic substances: A molecular dynamics studyENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 1 2010Ludmilla Aristilde Abstract A comprehensive assessment of the potential impacts of antimicrobials released into the environment requires an understanding of their sequestration by natural particles. Of particular interest are the strong interactions of antimicrobials with natural organic matter (NOM), which are believed to reduce their bioavailability, retard their abiotic and biotic degradation, and facilitate their persistence in soils and aquatic sediments. Molecular dynamics (MD) relaxation studies of a widely used fluoroquinolone antibiotic, ciprofloxacin (Cipro), interacting with a model humic substance (HS) in a hydrated environment, were performed to elucidate the mechanisms of these interactions. Specifically, a zwitterionic Cipro molecule, the predominant species at circumneutral pH, was reacted either with protonated HS or deprotonated HS bearing Ca, Mg, or Fe(II) cations. The HS underwent conformational changes through rearrangements of its hydrophobic and hydrophilic regions and disruption of its intramolecular H-bonds to facilitate favorable intermolecular H-bonding interactions with Cipro. Complexation of the metal cations with HS carboxylates appeared to impede binding of the positively charged amino group of Cipro with these negatively charged HS complexation sites. On the other hand, an outer-sphere complex between Cipro and the HS-bound cation led to ternary Cipro,metal,HS complexes in the case of Mg,HS and Fe(II),HS, but no such bridging interaction occurred with Ca,HS. The results suggested that the ionic potential (valence/ionic radius) of the divalent cation may be a determining factor in the formation of the ternary complex, with high ionic potential favoring the bridging interaction. Environ. Toxicol. Chem. 2010;29:90,98. © 2009 SETAC [source] Sorption irreversibility of 1,4-dichlorobenzene in two natural organic matter,rich geosorbentsENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 3 2009Michael Sander Abstract Hysteresis, a frequently observed phenomenon in sorption studies, is inconsistent with the key assumption of sorption reversibility in most fate and bioavailability models. Therefore, a study of the underlying causes of hysteresis is essential. Carbon-radiolabeled 1,4-dichlorobenzene (DCB) isotope tracer exchange was carried out at select points along the isotherms of DCB in a brown coal and a peat soil, holding total DCB concentration constant. Tracer exchange was performed both in the forward (sorption) and reverse (desorption) directions at the bulk sorption points and in the desorption direction at the corresponding bulk desorption points. Bulk DCB isotherms showed concentration-dependent hysteresis. However, tracer reequilibration in all cases was consistent with free exchange between sorbed and aqueous-phase molecules. These results rule out common experimental artifacts and demonstrate that sorption of bulk DCB is truly hysteretic (i.e., irreversible). The differences in rates between bulk and tracer sorption and desorption are consistent with the coupling of bulk DCB diffusion to other processes that retard equilibration, which we assign to matrix swelling or shrinking. Hysteresis is attributed to matrix deformation,specifically, to inelastic expansion and creation of voids accommodating sorbate molecules in the matrix, which leads to enhanced affinity in the desorption step. Comparing the results to previous results for naphthalene in the coal, we find that irreversible effects are similar for DCB and naphthalene in the coal but differ for DCB between the two sorbents. An explanation based on the different physical properties of these sorbents is provided. Solid-phase extraction of equilibrated DCB with Tenax® revealed a highly desorption-resistant fraction. While too small to account for the observed hysteresis, this fraction may represent molecules that become trapped as the matrix collapses and simultaneously stiffens during abrupt desorption. [source] Molecular modeling of metal complexation by a fluoroquinolone antibioticENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 11 2008Ludmilla Aristilde Abstract An understanding of the factors controlling the chemodynamics of fluoroquinolone antibiotics in different environmental matrices is a necessary prerequisite to the assessment of their potential impact on nontarget organisms in soils and receiving waters. Of particular interest are the complexes formed between fluoroquinolones and metal cations, which are believed to be important in the mechanism of sequestration of the antibiotic by minerals and natural organic matter. The structures of these complexes have not been fully resolved by conventional spectroscopy; therefore, molecular simulations may provide useful complementary insights. We present results from apparently the first molecular dynamics simulations of a widely used fluoroquinolone antibiotic, ciprofloxacin (Cipro), in aqueous complexes with five metal cations typically found in soils and surface waters: Ca2+, Mg2+, Fe2+, Na+, and K+. The interatomic potential functions employed in the simulations were validated by comparison with available structural data for solid-phase Cipro-hexahydrate and for the metal cations in aqueous solution. Although no comprehensive structural data on the aqueous complexes appear to be available, properties of the metal complexes predicted by our simulations agree with available data for solid-phase metal,Cipro complexes. Our results indicate that the ionic potential of the metal cation controls the stability of the complex formed and that the hydration number of the metal cation in aqueous solution determines its coordination number with O atoms in the metal,Cipro complex. In respect to environmental chemodynamics, our results imply that Cipro will form two configurations of bidendate chelates with metal centers on exposed surfaces of mineral oxides, water-bridged surface complexes with exchangeable cations in clay mineral interlayers, and cation-bridged complexes with functional groups in natural organic matter. [source] Factors influencing the partitioning and toxicity of nanotubes in the aquatic environment,,ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 9 2008Alan J. Kennedy Abstract Carbon nanotubes (NTs) may be among the most useful engineered nanomaterials for structural applications but could be difficult to study in ecotoxicological evaluations using existing tools relative to nanomaterials with a lower aspect ratio. Whereas the hydrophobicity and van der Waals interactions of NTs may suggest aggregation and sedimentation in aquatic systems, consideration regarding how engineered surface modifications influence their environmental fate and toxicology is needed. Surface modifications (e.g., functional groups and coatings) are intended to create conditions to make NTs dispersible in aqueous suspension, as required for some applications. In the present study, column stability and settling experiments indicated that raw, multiwalled NTs (MWNTs) settled more rapidly than carbon black and activated carbon particles, suggesting sediment as the ultimate repository. The presence of functional groups, however, slowed the settling of MWNTs (increasing order of stability: hydroxyl > carboxyl > raw), especially in combination with natural organic matter (NOM). Stabilized MWNTs in high concentrations of NOM provided relevance for water transport and toxicity studies. Aqueous exposures to raw MWNTs decreased Ceriodaphnia dubia viability, but such effects were not observed during exposure to functionalized MWNTs (>80 mg/L). Sediment exposures of the amphipods Leptocheirus plumulosus and Hyalella azteca to different sizes of sediment-borne carbon particles at high concentration indicated mortality increased as particle size decreased, although raw MWNTs induced lower mortality (median lethal concentration [LC50], 50 to >264 g/kg) than carbon black (LC50, 18,40 g/kg) and activated carbon (LC50, 12,29 g/kg). Our findings stress that it may be inappropriate to classify all NTs into one category in terms of their environmental regulation. [source] Copper toxicity in relation to surface water-dissolved organic matter: Biological effects to Daphnia magnaENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 12 2004Kees J.M. Kramer Abstract Water quality standards for copper are usually stated in total element concentrations. It is known, however, that a major part of the copper can be bound in complexes that are biologically not available. Natural organic matter, such as humic and fulvic acids, are strong complexing agents that may affect the bioavailable copper (Cu2+) concentration. The aim of this study was to quantify the relation between the concentration of dissolved natural organic matter and free Cu2+ in surface waters, and the biological effect, as measured in a standardized ecotoxicological test (48 h-median effective concentration [EC50] Daphnia magna, mobility). Six typical Dutch surface waters and an artificial water, ranging from 0.1 to 22 mg/L dissolved organic carbon (DOC), were collected and analyzed quarterly. Chemical speciation modeling was used as supporting evidence to assess bioavailability. The results show clear evidence of a linear relation between the concentration of dissolved organic carbon (in milligrams DOC/L) and the ecotoxicological effect (as effect concentration, EC50, expressed as micrograms Cu/L): 48-h EC50 (Daphnia, mobility) = 17.2 × DOC + 30.2 (r2 = 0.80, n = 22). Except for a brook with atypical water quality characteristics, no differences were observed among water type or season. When ultraviolet (UV)-absorption (380 nm) was used to characterize the dissolved organic carbon, a linear correlation was found as well. The importance of the free copper concentration was demonstrated by speciation calculations: In humic-rich waters the free Cu2+ concentration was estimated at ,10,11 M, whereas in medium to low dissolved organic carbon waters the [Cu2+] was ,10,10 M. Speciation calculations performed for copper concentrations at the effective concentration level (where the biological effect is considered the same) resulted in very similar free copper concentrations (,10,8 M Cu) in these surface waters with different characteristics. These observations consistently show that the presence of organic matter decreases the bioavailability, uptake, and ecotoxicity of copper in the aquatic environment. It demonstrates that the DOC content must be included in site-specific environmental risk assessment for trace metals (at least for copper). It is the quantification of the effects described that allows policy makers to review the criteria for copper in surface waters. [source] Influence of water quality and age on nickel toxicity to fathead minnows (Pimephales promelas)ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 1 2004Tham Chung Hoang Abstract This research characterized the effects of water quality and organism age on the toxicity of nickel (Ni)to fathead minnows (Pimephales promelas) to facilitate the accurate development of site-specific water-quality criteria. Nickel sulfate hexa-hydrate (NiSO4·6H2O) was used as the Ni source for performing acute toxicity tests (median lethal concentration after 96-h exposure [96-h LC50]) with <1-d-old and 28-d-old P. promelas under varying regimes of hardness, pH, alkalinity, and natural organic matter (NOM). The toxicity of Ni was inversely related to water hardness between hardness values of 20 and 150 mg/L (as CaCO3). Below 30 mg/L alkalinity, Ni toxicity was related to alkalinity. The effect of pH was confounded by hardness and the presence of NOM. In the absence of NOM, the toxicity of Ni increased as pH increased at high hardness and alkalinity. In general, 28-d-old fish were less sensitive than <1-d-old fish to Ni. This lower sensitivity ranged from 12-fold at low hardness and alkalinity (20 and 4 mg/L, respectively) to 5-fold at high hardness and alkalinity (100 and 400 mg/L, respectively). The presence of NOM (10 mg/L as dissolved organic carbon [DOC]) reduced Ni toxicity by up to 50%, but this effect appeared to be saturated above DOC at 5 mg/L. Incubating Ni with the NOM solution from 1 to 17 days had no effect on Ni toxicity. When using multivariate analysis, the 96-h LC50 for Ni was a function offish age, alkalinity, hardness, and NOM (96-h LC50 = ,0.642 + 0.270(fish age) + 0.005(alkalinity) + 0.018(hardness) + 0.138(DOC)). When using this model, we found a strong relationship between measured and predicted 96-h LC50 values (r2 = 0.94) throughout the treatment water qualities. The biotic ligand model (BLM) did not accurately predict Ni toxicity at high or low levels of alkalinity. Results of our research suggest that the BLM could be improved by considering NiCO3 to be bioavailable. [source] Biotic ligand model of the acute toxicity of metals.ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 10 2001Abstract The biotic ligand model (BLM) was developed to explain and predict the effects of water chemistry on the acute toxicity of metals to aquatic organisms. The biotic ligand is defined as a specific receptor within an organism where metal complexation leads to acute toxicity. The BLM is designed to predict metal interactions at the biotic ligand within the context of aqueous metal speciation and competitive binding of protective cations such as calcium. Toxicity is defined as accumulation of metal at the biotic ligand at or above a critical threshold concentration. This modeling framework provides mechanistic explanations for the observed effects of aqueous ligands, such as natural organic matter, and water hardness on metal toxicity. In this paper, the development of a copper version of the BLM is described. The calibrated model is then used to calculate LC50 (the lethal concentration for 50% of test organisms) and is evaluated by comparison with published toxicity data sets for freshwater fish (fathead minnow, Pimephales promelas) and Daphnia. [source] Utilization of oligo- and polysaccharides at microgram-per-litre levels in freshwater by Flavobacterium johnsoniaeJOURNAL OF APPLIED MICROBIOLOGY, Issue 4 2010E.L.W. Sack Abstract Aims:, To obtain a bacterial strain that can be used to quantify biodegradable polysaccharides at concentrations of a few micrograms per litre in freshwater. Methods and Results:,Flavobacterium johnsoniae strain A3 was isolated from tap water supplemented with laminarin, pectin or amylopectin at 100 ,g C l,1 and river Rhine water. The organism utilized 14 of 23 oligo- and polysaccharides, and 1 of 9 monosaccharides, but none of the sugar acids, sugar alcohols, carboxylic acids or aromatic acids tested at 10 ,g C l,1. Amino acids promoted growth of strain A3, but not in coculture with assimilable organic carbon (AOC) test strain Pseudomonas fluorescens P17, which utilized these compounds more rapidly than strain A3. Compounds released by strain P17 and AOC test strain Spirillum sp. NOX grown on acetate promoted the growth of strain A3 at Nmax values of , 2 × 105 CFU ml,1 of strain P17 and , 5 × 105 CFU ml,1 of strain NOX. Significant growth of strain A3 was observed in surface water and in tap water in the presence of strain P17 (Nmax P17 < 2 × 105 CFU ml,1). Conclusions:, Strain A3 utilizes oligo- and polysaccharides at microgram-per-litre levels. In surface water and in tap water, the organism was able to utilize compounds that were not utilized by strain P17. These compounds may include oligo- and/or polysaccharides. Significance and Impact of the Study:, Phytoplanktonic and bacterial polysaccharides can constitute an important biodegradable fraction of natural organic matter in water and may promote growth of heterotrophic bacteria during water treatment and drinking water distribution. Strain A3 can be used to quantify a group of compounds that includes oligo- and polysaccharides at microgram-per-litre levels in freshwater. [source] Sensing of toxic metals through pH changes using a hybrid sorbent material: Concept and experimental validationAICHE JOURNAL, Issue 11 2009Prasun K. Chatterjee Abstract This article reports a new hybrid sorbent material that is capable of detecting trace concentration of toxic metals, such as zinc, lead, copper, nickel, etc., through pH changes only. The material is essentially a composite granular material synthesized through rapid fusion of a mixture of amorphous hydrated ferric oxide (HFO) and akermanite or calcium magnesium silicate (Ca2MgSi2O7). When a water sample is rapidly passed through a mini-column containing this hybrid material, effluent pH at the exit always remains alkaline (,9.0) because of slow hydrolysis of akermanite and steady release of hydroxyl (OH,) ions. This exit solution turns pink through the addition of a phenolphthalein indicator. Commonly encountered electrolytes containing sodium, calcium, chloride, and sulfate have no impact on the exit pH from the mini-column. However, when trace concentration of a heavy metal (say lead) is present in the sample water, a considerable drop in pH (>2 units) is observed for the exiting solution. At this point, the solution turns colorless through the addition of a phenolphthalein indicator. Moreover, the change in the slope of pH, i.e., ,dpH/dBV, provides a sharp, noticeable peak for each toxic metal where BV is the bed volumes of solution fed. The technique allowed detection of zinc and lead through pH swings in synthesized samples, spiked Bethlehem City water, and also in Lehigh River water in the presence of phosphate and natural organic matter (NOM). Using a simple preconcentration technique, lower than 10 ,g/l of lead was detected with a significant peak. From a mechanistic viewpoint, high sorption affinity of HFO surface sites toward toxic metal cations, ability of akermanite to maintain near-constant alkaline pH for a prolonged period through slow hydrolysis and labile metal-hydroxy complex formation causing dissipation of OH, ions from the aqueous phase provide a synergy that allows detection of toxic metals at concentrations well below 100 ,g/l through pH changes. Nearly all previous investigations pertaining to toxic metals sensing use metal-selective enzymes or organic chromophores. This simple-to-operate technique using an inexpensive hybrid material may find widespread applications in the developing world for rapid detection of toxic metals through pH changes. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Soil organic matter beyond molecular structure Part I: Macromolecular and supramolecular characteristicsJOURNAL OF PLANT NUTRITION AND SOIL SCIENCE, Issue 2 2006Gabriele E. Schaumann Abstract This contribution reviews and discusses structural aspects of soil organic matter (SOM) and humic substances (HS) with special respect to the macromolecular and the supramolecular view. It can be concluded that (1) dissolved humic acids behave as supramolecular associations of relatively small molecules with an enormous flexibility of reaction of environmental conditions, (2) multivalent cations may increase the apparent molecular weight by the formation of coordinative crosslinks in dissolved and undissolved natural organic matter (NOM), (3) sorption nonlinearity in solid humic acids and SOM may be due to polymer properties of NOM, (4) sorbates affect sorbent characteristics of SOM, and (5) hysteresis and conditioning effects in SOM can up to now best be explained with the polymer analogy. A distinct polydispersivity of SOM over a wide range of molecular masses is to be assumed. The supramolecular and the macromolecular models were derived from humic acids with different composition and on the basis of different sample states. Although the supramolecular model has not explicitely been shown for unfractionated DOM, the combination of all discussed studies suggests supramolecular as well as macromolecular characteristics of NOM. Neither macromolecules nor small molecules can be fully excluded in solid and dissolved SOM. Microregions with different properties provide different types of sorption sites. SOM is suggested to be regarded as amorphous material. This point of view is not restricted to high molecular masses and may supplement our understanding of SOM by the model of physical aging. [source] Sorption of polycyclic aromatic hydrocarbons into liposomes (artificial cell membranes) and the effects of dissolved natural organic matterLAKES & RESERVOIRS: RESEARCH AND MANAGEMENT, Issue 4 2002Yoshihisa Shimizu Abstract Dissolved natural organic matter (NOM) occurs widely in the aquatic environment and affects the fate of microorganic pollutants (e.g. intake, accumulation, movement, degradation, toxicity). The effect of NOM on the intake into biota (living cells) is very important. In the present study, the effects of coexisting NOM on the intake of microorganic pollutants into aquatic biota were experimentally evaluated. The NOM was concentrated from Lake Biwa water using a reverse osmosis filtration membrane. Two polycyclic aromatic hydrocarbons (PAH; pyrene and phenanthrene) were used as representative microorganic pollutants. Liposomes were synthesized in the laboratory to simulate living cell membranes and were used to investigate the intake of microorganic pollutants into aquatic biota. The experimental results (PAH onto NOM, NOM into liposomes, and PAH into liposomes) indicated that the sorption of PAH into liposomes was suppressed, apparently by PAH binding with NOM in the aqueous phase. This suggests that the accumulation and/or toxicity of microorganic pollutants can be retarded by NOM in the aqueous environment. Moreover, the experimental results indicated that sorption into liposomes (the liposome/water sorption coefficient, Klipw) could be a better parameter for estimating the intake of microorganic pollutants into aquatic biota than the n-octanol/water partition coefficient (Kow) in the aqueous environment. [source] Identifying residues in natural organic matter through spectral prediction and pattern matching of 2D NMR datasetsMAGNETIC RESONANCE IN CHEMISTRY, Issue 1 2004Andre J. Simpson Abstract This paper describes procedures for the generation of 2D NMR databases containing spectra predicted from chemical structures. These databases allow flexible searching via chemical structure, substructure or similarity of structure as well as spectral features. In this paper we use the biopolymer lignin as an example. Lignin is an important and relatively recalcitrant structural biopolymer present in the majority of plant biomass. We demonstrate how an accurate 2D NMR database of ,600 2D spectra of lignin fragments can be easily constructed, in ,2 days, and then subsequently show how some of these fragments can be identified in soil extracts through the use of various search tools and pattern recognition techniques. We demonstrate that once identified in one sample, similar residues are easily determined in other soil extracts. In theory, such an approach can be used for the analysis of any organic mixtures. Copyright © 2003 John Wiley & Sons, Ltd. [source] Non-disturbing characterization of natural organic matter (NOM) contained in clay rock pore water by mass spectrometry using electrospray and atmospheric pressure chemical ionization modesRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 2 2010Sandrine Huclier-Markai We have investigated the composition of the mobile natural organic matter (NOM) present in Callovo-Oxfodian pore water using electrospray ionization mass spectrometry (ESI-MS), atmospheric pressure chemical ionization mass spectrometry (APCI-MS) and emission-excitation matrix (EEM) spectroscopy. The generation of knowledge of the composition, structure and size of mobile NOM is necessary if one wants to understand the interactions of these compounds with heavy metals/radionuclides, in the context of environmental studies, and particularly how the mobility of these trace elements is affected by mobile NOM. The proposed methodology is very sensitive in unambiguously identifying the in situ composition of dissolved NOM in water even at very low NOM concentration, due to innovative non-disturbing water sampling and ionization (ESI/APCI-MS) techniques. It was possible to analyze a quite exhaustive inventory of the small organic compounds of clay pore water without proceeding to any chemical treatment at naturally occurring concentration levels. The structural features observed were mainly acidic compounds and fatty acids as well as aldehydes and amino acids. Copyright © 2009 John Wiley & Sons, Ltd. [source] Sequestration of organometallic compounds by natural organic matter. binding of trimethyltin(IV) by fulvic and alginic acidsAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 10 2006Alba Giacalone Abstract The binding capacity of fulvic and alginic acids towards trimethyl tin(IV) cation was quantitatively determined in order to evaluate the sequestering ability of toxic organometallic compounds by natural organic matter. Investigations were performed in the pH range of natural waters (5,8.5) where the carboxylate groups, largely present in both sequestering agents, are the main binding sites. A chemical interaction model, according to which both the protonation of polyelectrolyte ligands and the hydrolysis of the organotin cation in NaCl aqueous solution were considered, was used to define the speciation of the systems under investigation. Measurements performed at different ionic strength values (0.1, 0.25, 0.5 and 0.7 mol L,1, NaCl) allowed us to consider the dependence of stability constants on the ionic strength, and to calculate the formation constants at infinite dilution. Results obtained show the formation of the complex species TMT(L), TMT(L)2 and TMT(L)(OH) for L = fulvic acid and TMT(L) for L = alginic acid, respectively. In order to compare the strength of interaction of these natural poly electrolytes with other analogous synthetic polyelectrolytes, measurements were also carried out on the trimethyltin(IV),polyacrylate (5.1 kDa) system, and in this case the formation of TMT(L), TMT(L)2 and TMT(L)(OH) species was found. Results show the following trend of stability for the species TMT(L) in the systems investigated: TMT,fulvate , TMT,polyacrylate > TMT,alginate. On the basis of the stability data obtained, the lowest concentration of fulvic and alginic acids, able to act as sequestering agents towards triorganotin(IV) cation in the conditions of natural waters, was also calculated. Copyright © 2006 John Wiley & Sons, Ltd. [source] | ||||||||||||||||