Adsorption of natural dissolved organic matter at the oxide/water interface

Natural organic matter is readily adsorbed by alumina and kaolinite in the pH range of natural waters. Adsorption occurs by complex formation between surface hydroxyls and the acidic functional groups of the organic matter. Oxides with relatively acidic surface hydroxyls, e.g. silica, do not react strongly with the organic matter. Under conditions typical for natural waters, almost complete surface coverage by adsorbed organic matter may be expected for alumina, hydrous iron oxides and the edge sites of aluminosilicates. Potentiometric titration and electrophoresis indicate that most of the acidic functional groups of the adsorbed organic matter are neutralized by protons from solution. The organic coating is expected to have a great influence on subsequent adsorption of inorganic cations and anions.     

Influence of the natural organic matter in the removal of caffeine from water by fixed-bed column adsorption

The removal of caffeine from tap water by F-400 granular activated carbon in fixed-bed adsorption experiments was carried out. Textural and chemical characterization of the adsorbent through N₂ adsorption–desorption isotherms, Fourier transform infrared spectrometry, isoelectric point determination and scanning electron microscopy studies was developed in studies previously reported. Caffeine breakthrough curves and total organic carbon profiles at different operation conditions (inlet concentration, volumetric flow rate and mass of adsorbent) were obtained. These experimental results showed a displacement of the natural organic matter from the active sites exerted by caffeine molecules due to their higher affinity to the surface carbon. This behavior led to an overshooting, a local outlet natural organic matter concentration higher than the feed quantity. A competitive effect seems to be observed in the removal of the target compound, decreasing the efficiency of the process. Axial dispersion coefficients and dimensionless numbers were estimated for the caffeine removal onto F-400 activated carbon. Therefore, the regeneration of the adsorbent by adsorption–desorption cycles was studied.     

Characterizing the molecular structure of organic matter from natural environments: An analytical challenge

Natural organic matter (OM) is widespread in terrestrial ecosystems and it plays a major role in the global carbon cycle. Despite this high environmental importance, its characterization at the molecular level remains unsatisfactory, especially when the macromolecular OM is concerned. Such a characterization is challenging because of the diversity and heterogeneity of OM, but it is of prime importance to derive OM reactivity and, more generally, to model environmental processes in which natural OM is involved. This awareness led to a wealth of analytical developments, which are described in the present review. They include improvements of existing techniques, but also new approaches and concern spectroscopic tools along with chemical and thermal degradations.     

Models of natural organic matter and interactions with organic contaminants

Adsorption of organic contaminants onto soils, sediments and other particulates has the potential to be a major controlling factor in their bioavailability, fate and behavior in the environment. Models for estimating the amount and stability of sorbed organic contaminants based on the fraction of organic carbon in a soil or sediment can oversimplify the process of sorption in the environment. In order to help understand sorption of organic contaminants in soils and sediments, we modeled various components of natural organic matter (NOM) that are possible substrates for sorption. These substrates include soot particles, lignin, humic and fulvic acids. The molecular scale interactions of selected aromatic hydrocarbons with different substrates were also simulated. Results of the simulations include the 3-D structures of the NOM components, changes in structure with protonation state and solvation and the sorption energy between PAH and substrate. This last parameter is an indicator of the amount of contaminant that will sorb and the energy required to free the contaminant from the substrate. Although the simulation results presented in this paper represent a first-order examination of NOM and contaminant interactions, the findings highlight a number of essential features that should be included in future molecular models of NOM and contaminant sorption.     

Diagenesis and formation water chemistry of Triassic reservoir sandstones from southern Tunisia

The fluvial Triassic reservoir subarkoses and arkoses (2409·5–2519·45 m) of the El Borma oilfield, southern Tunisia, were subjected to cementation by haematite, anatase, infiltrated clays, kaolinite and K-feldspar at shallow burial depths from meteoric waters. Subsequently, basinal brines controlled the diagenetic evolution of the sandstones and resulted initially in the precipitation of quartz overgrowths, magnesian siderite, minor ferroan magnesite and anhydrite. The enrichment of siderite in ¹²C isotope (δ¹³C_PDB= - 14·5 to - 9‰) results from derivation of carbon from the thermal decarboxylation of organic matter. During further burial, the precipitation of dickite and pervasive transformation of kaolinite into dickite occurred, followed by the formation of microcrystalline K-feldspar and quartz, chlorite and illite, prior to the emplacement of oil. Present day formation waters are Na-Ca-Cl brines evolved by the evaporation of seawater and water/mineral interaction and are in equilibrium with the deep burial (≤ 3·1 km) minerals. These waters are suggested to be derived from the underlying Silurian and Devonian dolomitic mudstones.     

Land-derived organic matter in surface sediments from the Gulf of Mexico

Lignin oxidation products and ¹³C/¹²C ratios were compared as indicators of land-derived organic matter in surface sediments from the western Gulf of Mexico. Whole sediments were reacted with cupric oxide to yield phenolic oxidation products that indicated the types and relative amounts of the lignins that were present.Measurements of lignin concentration and carbon isotope abundances both indicated a sharp offshore decrease of land-derived organic matter in most areas of the western Gulf. This decrease results primarily from mixing of terrestrial and marine organic matter. The terrestrially derived material in these sediments has a lignin content similar to that of grasses and tree leaves. Flowering plants contribute most of the sedimented lignin compounds. These lignins apparently occur in the form of well-mixed plant fragments that are transported to sea by rivers and deposited primarily on the inner continental shelf.     

Dissolved organic matter in pore water of carbonate sediments from Bermuda

Pore water samples from seven nearshore areas in Bermuda were obtained under in situ conditions and analyzed for dissolved organic carbon, dissolved carbohydrates, dissolved free amino acids and dissolved humic substances. The concentration of dissolved organic carbon is higher than in the overlying nearshore waters indicating significant diagenetic remobilization of carbon in these recently deposited carbonate sediments. Dissolved carbohydrates decrease with depth due to microbial utilization.     

Effects of water chemistry and concentrations of dissolved organic matter on its fluorescence characteristics and molecular conformation

Previous studies showed that water chemistry and concentrations of dissolved organic matter (DOM) could affect its molecular conformation and binding characteristics with hydrophobic organic contaminants (HOCs). However, the conformational change of DOM resultant from water chemistry and concentrations of DOM was not extensively investigated; therefore, the contradictory reports regarding the binding property with HOCs were available in literature. In this study, the effects of ionic strength, pH and DOM concentrations on the fluorescence properties of two humic acids (HA), namely Fluka HA and Amherst HA, were investigated by three-dimensional excitation-emission matrix fluorescence spectroscopy (3DEEM) and steady-state fluorescence polarization (FP) techniques. The results not only corroborated previous observations obtained by other investigators, but revealed some new information about the fluorescence properties and molecular conformation of the humic acids under different water chemistry and DOM concentration conditions, which could shed light on its binding mechanisms and binding properties with HOCs.     

The distribution and source of organic matter in reservoir sediments

The bottom sediments of two reservoirs, one with significant river sediment input and one without, were analyzed for organic matter content. Lake Texoma sediments average 1.0% organic carbon, of which 0.26% organic carbon is deposited by the river sediments of the Red and Washita River deltas. In Fort Gibson reservoir, where there is minimal river sediment input, the organic carbon averages 1.2% and is deposited with a strong correlation to water depth (+0.9). There is a significant difference between the C/N ratio of Lake Texoma sediments (11.5) and Fort Gibson sediments (9.6). The higher C/N ratio is suggested to be a result of the larger input of terrestrial plant debris (with a high original C/N ratio) by the rivers draining into Lake Texoma and the relatively high resistance of the lignin material in the plant debris to decomposition in the reservoir sediments.     

Removal of bisphenol A from aqueous solution using cetylpyridinium bromide (CPB)-modified natural zeolites as adsorbents

Surfactant-modified natural zeolites (SMNZs) with different coverage types were prepared by loading cetylpyridinium bromide onto the surface of natural zeolites. The resulting SMNZs were characterized and used as adsorbents to remove bisphenol A (BPA) from aqueous solution. The monolayer and bilayer SMNZs were effective for removing BPA from aqueous solution. The BPA adsorption capacity for the monolayer SMNZ increased slightly with increasing pH from 4 to 9, but decreased significantly with increasing pH from 9 to 11. The BPA adsorption capacity for the bilayer SMNZ was relatively high at pH 9–10, but decreased with decreasing pH from 9 to 4 or increasing pH from 10 to 11. The equilibrium adsorption data of BPA on the monolayer and bilayer SMNZs under the experimental condition could be well described by the Langmuir and Freundlich isotherm models. The adsorption kinetics of BPA on the monolayer and bilayer SMNZs followed a pseudo-second-order model. The adsorption of BPA on the monolayer and bilayer SMNZs took place in three different stages: a fast external surface adsorption, a gradual adsorption controlled by both the external mass transfer and the intra-particle diffusion, and a final equilibrium stage. The adsorption of BPA on the monolayer and bilayer SMNZs is spontaneous and exothermic. The mechanisms for BPA adsorption onto the monolayer SMNZ at pH 4–11 include the hydrophobic interaction and hydrogen bonding. The mechanisms for BPA adsorption onto the bilayer SMNZ at pH 4–8 include the organic partitioning and hydrogen bonding. The mechanisms for BPA adsorption onto the bilayer SMNZ at pH 8–11 include the organic partitioning, hydrogen bonding and electrostatic attraction.     

Heterogeneous organic matter from the surface horizon of a temperate zone marsh

Abundance, bulk chemical composition and sources of the organic matter in the surface horizon of the permanently water-covered part of an intermittently water-covered marsh were investigated. Lipids, insoluble non-hydrolysable macromolecular organic matter and black carbon fractions were isolated and examined via Rock-Eval pyrolysis, elemental analysis, Fourier transform infrared spectroscopy, isotopic (δ¹³C, δ¹⁵N) methods and high resolution transmission electron microscopy. Integration of bulk Rock-Eval data, elemental and isotopic composition, together with spectroscopic features, suggested immature Type III organic matter derived mainly from C₃ vascular plants. The distribution of n-alkanes from the non-aromatic lipid fraction exhibited the importance of emergent macrophytes and terrestrial plants, as well as a moderate input of submerged/floating macrophytes to the source biomass. Mathematical deconvolution of a Rock-Eval pyrogram revealed highly heterogeneous organic matter composed of a mixture of thermally labile biopolymers (36%) at various stages of decomposition, as well as humic substances and highly refractory organic matter (64%) in the whole sample. Markedly lower heterogeneity and aliphaticity, together with a higher proportion of humic substances and highly refractory organic matter (ca. 84%) were observed in the macromolecular fraction. An abundant contribution of black carbon to the macromolecular fraction was indicated by mathematical deconvolution of the Rock-Eval pyrogram and was clearly shown by the isolation of this fraction and chemical oxidation. The black carbon fraction appeared to account for ca. half of the macromolecular fraction, the carbon in these two fractions representing 30% and 14% of the initial carbon, respectively. The electron microscopy observations directly evidenced the presence of black carbon, which was comprised of both amorphous poorly organized particles and highly ordered onion-shaped particles.     

Sedimentary geochemistry of the Yangtze River： Sediment source-to-sink tracing implication

The Yangtze （Changjiang） River as the largest fiver originating from eastern Tibetan Plateau, has increasingly attracted considerable attention of many researchers for almost one hundred years. The fiver linking the Tibetan Plateau with the West Pacific Marginal Sea, encompasses variable source rocks and complicated drainage patterns and spans across distinct climate zones. The increasing human activities in the last 2000 years have significantly changed the weathering process and sediment source-to-sink pattern in the fiver basins. In terms of this, the Yangtze drainage basin as well as the deltaic and coastal areas can be regarded as one of the best regions in the world to investigate the source-to-sink process of continental sediments into the marginal sea. In the past ten years we systematically measured elemental and Sr-Nd-Pb isotopic compositions of the Yangtze riverine sediments which were collected from the mainstream and main tributaries. Analytical results clearly showed that the Yangtze sediments yield geochemical compositions different from those of other fiver sediments due to the very complicated source rock types and variable chemical weathering regimes in the large drainage basin. REE and Sr-Nd isotopic compositions suggest that the sediment source-to-sink pattern in the modern Yantze River basins varies considerably from the upper basin to the lower valley. Different chemical compositions among the main tributaries and the mainstream are responsible for the compositional variations of the Yangtze River sediments. It is a piece of quite challenging work to establish a sediment source-to-sink model to quantifying the contributions of the main tributaries to the mainstream.     

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.     

Complexation of trace metals by adsorbed natural organic matter

The adsorption behavior and solution speciation of Cu(II) and Cd(II) were studied in model systems containing colloidal alumina particles and dissolved natural organic matter. At equilibrium a significant fraction of the alumina surface was covered by adsorbed organic matter. Cu(II) was partitioned primarily between the surface-bound organic matter and dissolved Cu-organic complexes in the aqueous phase. Complexation of Cu²⁺ with the functional groups of adsorbed organic matter was stronger than complexation with uncovered alumina surface hydroxyls. It is shown that the complexation of Cu(II) by adsorbed organic matter can be described by an apparent stability constant approximately equal to the value found for solution phase equilibria. In contrast, Cd(II) adsorption was not significantly affected by the presence of organic matter at the surface, due to weak complex formation with the organic ligands. The results demonstrate that general models of trace element partitioning in natural waters must consider the presence of adsorbed organic matter.     

The nature of Cu bonding to natural organic matter

Copper biogeochemistry is largely controlled by its bonding to natural organic matter (NOM) for reasons not well understood. Using XANES and EXAFS spectroscopy, along with supporting thermodynamic equilibrium calculations and structural and steric considerations, we show evidence at pH 4.5 and 5.5 for a five-membered Cu(malate)₂-like ring chelate at 100-300 ppm Cu concentration, and a six-membered Cu(malonate))_1-2-like ring chelate at higher concentration. A “structure fingerprint” is defined for the 5.0-7.0 Å⁻¹ EXAFS region which is indicative of the ring size and number (i.e., mono- vs. bis-chelate), and the distance and bonding of axial oxygens (O_ax) perpendicular to the chelate plane formed by the four equatorial oxygens (O_eq) at 1.94 Å. The stronger malate-type chelate is a C₄ dicarboxylate, and the weaker malonate-type chelate a C₃ dicarboxylate. The malate-type chelate owes its superior binding strength to an -OH for -H substitution on the α carbon, thus offering additional binding possibilities. The two new model structures are consistent with the majority of carboxyl groups being clustered and α-OH substitutions common in NOM, as shown by recent infrared and NMR studies. The high affinity of NOM for Cu(II) is explained by the abundance and geometrical fit of the two types of structures to the size of the equatorial plane of Cu(II). The weaker binding abilities of functionalized aromatic rings also is explained, as malate-type and malonate-type structures are present only on aliphatic chains. For example, salicylate is a monocarboxylate which forms an unfavorable six-membered chelate, because the OH substitution is in the β position. Similarly, phthalate is a dicarboxylate forming a highly strained seven-membered chelate.Five-membered Cu(II) chelates can be anchored by a thiol α-SH substituent instead of an alcohol α-OH, as in thio-carboxylic acids. This type of chelate is seldom present in NOM, but forms rapidly when Cu(II) is photoreduced to Cu(I) at room temperature under the X-ray beam. When the sample is wet, exposure to the beam can reduce Cu(II) to Cu(0). Chelates with an α-amino substituent were not detected, suggesting that malate-like α-OH dicarboxylates are stronger ligands than amino acids at acidic pH, in agreement with the strong electronegativity of the COOH clusters. However, aminocarboxylate Cu(II) chelates may form after saturation of the strongest sites or at circumneutral pH, and could be observed in NOM fractions enriched in proteinaceous material. Overall, our results support the following propositions:

(1)

The most stable Cu-NOM chelates at acidic pH are formed with closely-spaced carboxyl groups and hydroxyl donors in the α-position; oxalate-type ring chelates are not observed.

(2)

Cu(II) bonds the four equatorial oxygens to the heuristic distance of 1.94 ± 0.01 Å, compared to 1.97 Å in water. This shortening increases the ligand field strength, and hence the covalency of the Cu-O_eq bond and stability of the chelate.

(3)

The chelate is further stabilized by the bonding of axial oxygens with intra- or inter-molecular carboxyl groups.

(4)

Steric hindrances in NOM are the main reason for the absence of Cu-Cu interactions, which otherwise are common in carboxylate coordination complexes.

     

Impact of natural water chemistry on public drinking water in Japan

Drinking water from Japan (Toyama, Kumamoto, Osaka, and Tokyo Prefecture) and France (Volvic water) was evaluated for taste and health properties using an index based on major and trace mineral content and organoleptic components. Although various reports point to calcium (Ca²⁺) as a key ingredient imparting good taste and magnesium (Mg²⁺) and sulfate (SO₄ ^2?) as causing unpleasant taste in drinking water, recent sensory threshold experiments have indicated that other major ions and minerals directly or indirectly contribute to good taste, including potassium (K), silica (SiO₂), and phosphorous (P). The present study examined major and trace constituents in water to accurately quantify water taste, flavor, and health effects in good-tasting (Volvic, Toyama, and Kumamoto water) and average-tasting water (Osaka and Tokyo water). Trace metal, volatile organic carbon, non-purgeable organic carbon and total inorganic carbon levels were evaluated as parameters influencing the sensory properties of the drinking water. All of the representative good-tasting water contained higher amounts of tasty minerals (Ca²⁺, K⁺, SiO₂) and lower amounts of unsavory, rough (Mg²⁺ and SO₄ ^2?), and bitter (Cl^?) minerals. Stiff diagrams of the water samples indicated that good-tasting water was generally bicarbonate (HCO₃ ^?) type. Seasonal variations in physicochemical parameters did not change the order of abundance of cations and anions but did affect the concentration of various ions present in the water. Trace metals also affected water flavor. Mn facilitates acetaldehyde formation and Fe is associated with polyphenolic oxidation and formation of organoleptic flavor constituents. Trihalomethanes (THMs) may also cause unpleasant drinking water flavors or odors. THMs concentrations for all samples were below 5.7 μg/L, meeting the safety and taste requirements for good drinking water. The Japanese samples were compared against Volvic water, which was used as a standard for good-tasting water. Total dissolved solids concentrations were below 300 mg/L for all specimens, in compliance with World Health Organization guidelines. The results are discussed on the basis of the balance between inorganic major ions and trace minerals and THMs concentration thresholds.     

Nanoparticles in natural systems II: The natural oxide fraction at interaction with natural organic matter and phosphate

Information on the particle size and reactive surface area of natural samples and its interaction with natural organic matter (NOM) is essential for the understanding bioavailability, toxicity, and transport of elements in the natural environment. In part I of this series (Hiemstra et al., 2010), a method is presented that allows the determination of the effective reactive surface area (A, m²/g soil) of the oxide particles of natural samples which uses a native probe ion (phosphate) and a model oxide (goethite) as proxy. In soils, the natural oxide particles are generally embedded in a matrix of natural organic matter (NOM) and this will affect the ion binding properties of the oxide fraction. A remarkably high variation in the natural phosphate loading of the oxide surfaces (Γ, μmol/m²) is observed in our soils and the present paper shows that it is due to surface complexation of NOM, acting as a competitor via site competition and electrostatic interaction. The competitive interaction of NOM can be described with the charge distribution (CD) model by defining a ≡NOM surface species. The interfacial charge distribution of this ≡NOM surface species can be rationalized based on calculations done with an evolved surface complexation model, known as the ligand and charge distribution (LCD) model. An adequate choice is the presence of a charge of −1 v.u. at the 1-plane and −0.5 v.u. at the 2-plane of the electrical double layer used (Extended Stern layer model).The effective interfacial NOM adsorption can be quantified by comparing the experimental phosphate concentration, measured under standardized field conditions (e.g. 0.01 M CaCl₂), with a prediction that uses the experimentally derived surface area (A) and the reversibly bound phosphate loading (Γ, μmol/m²) of the sample (part I) as input in the CD model. Ignoring the competitive action of adsorbed NOM leads to a severe under-prediction of the phosphate concentration by a factor ∼10 to 1000. The calculated effective loading of NOM is low at a high phosphate loading (Γ) and vice versa, showing the mutual competition of both constituents. Both constituents in combination usually dominate the surface loading of natural oxide fraction of samples and form the backbone in modeling the fate of other (minor) ions in the natural environment.Empirically, the effective NOM adsorption is found to correlate well to the organic carbon content (OC) of the samples. The effective NOM adsorption can also be linked to DOC. For this, a Non-Ideal Competitive adsorption (NICA) model is used. DOC is found to be a major explaining factor for the interfacial loading of NOM as well as phosphate. The empirical NOM-OC relation or the parameterized NICA model can be used as an alternative for estimating the effective NOM adsorption to be implemented in the CD model for calculation of the surface complexation of field samples. The biogeochemical impact of the NOM-PO₄ interaction is discussed.