Adsorption of natural organic matter from waters by iron coated pumice

Natural pumice particles were used as granular support media and coated with iron oxides to investigate their adsorptive natural organic matter (NOM) removal from waters. The impacts of natural pumice source, particle size fraction, pumice dose, pumice surface chemistry and specific surface area, and NOM source on the ultimate extent and rate of NOM removal were studied. All adsorption isotherm experiments were conducted employing the variable-dose completely mixed batch reactor bottle-point method. Iron oxide coating overwhelmed the surface electrical properties of the underlying pumice particles. Surface areas as high as 20.6m(2)g(-1) were achieved after iron coating of pumice samples, which are above than those of iron coated sand samples reported in the literature. For all particle size fractions, iron coating of natural pumices significantly increased their NOM uptakes both on an adsorbent mass- and surface area-basis. The smallest size fractions (<63 microm) of coated pumices generally exhibited the highest NOM uptakes. A strong linear correlation between the iron contents of coated pumices and their Freundlich affinity parameters (K(F)) indicated that the enhanced NOM uptake is due to iron oxides bound on pumice surfaces. Iron oxide coated pumice surfaces preferentially removed high UV-absorbing fractions of NOM, with UV absorbance reductions up to 90%. Control experiments indicated that iron oxide species bound on pumice surfaces are stable, and potential iron release to the solution is not a concern at pH values of typical natural waters. Based on high NOM adsorption capacities, iron oxide coated pumice may be a promising novel adsorbent in removing NOM from waters. Furthermore, due to preferential removal of high UV-absorbing NOM fractions, iron oxide coated pumice may also be effective in controlling the formation of disinfection by-products in drinking water treatment.     

Synthesis and characterisation of Pd-modified N-doped TiO2 for photocatalytic degradation of natural organic matter (NOM) fractions

Introduction

The removal of natural organic matter (NOM) from water is becoming increasingly important in order to prevent the formation of carcinogenic disinfection by-products. The inadequate removal of NOM has a bearing on the capacity of the other treatment processes to remove organic micro-pollutants or inorganic species that may be present in the water. New methods are therefore currently being sought to effectively characterise NOM and also to ensure that it is sufficiently removed from drinking water sources.

Methodology

Nitrogen- and palladium-co-doped TiO₂ was synthesised by a modified sol?Cgel method and evaluated for its photocatalytic degradation activity on NOM fractions under simulated solar radiation. The photocatalyst was characterised by FT-IR, Raman, XRD, DRUV?Cvis, SEM, TEM, EDS, XPS and TGA. FT-IR confirmed the presence of OH groups on thermally stable, nearly spherical anatase nanoparticles with an average diameter of 20?nm. PdO species appeared on the surface of the TiO₂ as small uniformly dispersed particles (2 to 3?nm). A red shift in the absorption edge compared to commercial anatase TiO₂ was confirmed by DRUV?Cvis. In order to gain a better insight into the response of NOM to photodegradation, the NOM was divided into three different fractions based on its chemical nature.

Results and discussion

Photodegradation efficiencies of 96, 38 and 15?% were realised for the hydrophobic, hydrophilic and transphilic NOM fractions, respectively. A reasonable mechanism was proposed to explain the photocatalytic degradation of the NOM fractions. The high photocatalytic activity could be attributed to the larger surface area, smaller crystalline size and synergistic effects of the co-dopants N and Pd in the TiO₂ crystal.     

Comparative kinetic desorption of 60Co, 85Sr and 134Cs from a contaminated natural silica sand column: influence of varying physicochemical conditions and dissolved organic matter

In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces.     

Advanced oxidation of natural organic matter using hydrogen peroxide and iron-coated pumice particles

The oxidative removal of natural organic matter (NOM) from waters using hydrogen peroxide and iron-coated pumice particles as heterogeneous catalysts was investigated. Two NOM sources were tested: humic acid solution and a natural source water. Iron coated pumice removed about half of the dissolved organic carbon (DOC) concentration at a dose of 3000 mg l(-1) in 24 h by adsorption only. Original pumice and peroxide dosed together provided UV absorbance reductions as high as 49%, mainly due to the presence of metal oxides including Al(2)O(3), Fe(2)O(3) and TiO(2) in the natural pumice, which are known to catalyze the decomposition of peroxide forming strong oxidants. Coating the original pumice particles with iron oxides significantly enhanced the removal of NOM with peroxide. A strong linear correlation was found between iron contents of coated pumices and UV absorbance reductions. Peroxide consumption also correlated with UV absorbance reduction. Control experiments proved the effective coating and the stability of iron oxide species bound on pumice surfaces. Results overall indicated that in addition to adsorptive removal of NOM by metal oxides on pumice surfaces, surface reactions between iron oxides and peroxide result in the formation of strong oxidants, probably like hydroxyl radicals, which further oxidize both adsorbed NOM and remaining NOM in solution, similar to those in Fenton-like reactions.     

Reduced analytical availability of polychlorinated biphenyls (PCB's) in colored surface water

It has been generally accepted, during the last few decades, that the dissolved natural organic matter in water [DNOM] appearing as yellow brownish color, has become more and more "polluted" by inorganic and organic micro-pollutants. Due to the complexing properties of NOM, lipophilic organic micro-pollutants, such as, PCBs will be mobilized into water together with the DNOM. A mixture of eight PCBs, with Cl-content from tri-Cl to hepta-Cl, was added to solutions of ten different DNOMs. The DNOMs were aqua's solutions of RO-(reverse osmosis)-isolated material, having approximately the same concentration of carbon. After a contact time of three days, standard analytical PCB-method was used to determine the recovery of the added PCBs. The results show that the analytical availability of the added PCB was significantly reduced in the presence DNOM, compared to distilled water. The percentage loss in recovery of PCB increased with the content of Cl, in mean, from 3%/mg C for tri-Cl to 9%/mg C for hepta-Cl. The results also suggest that the analytical recovery of PCB was affected by the quality and the nature of the organic matter. For example the longer the DNOMs had been in the aquatic phase, the less efficient they are attached to the PCBs.     

Influence of the colloid type on the transfer of 60Co and 85Sr in silica sand column under varying physicochemical conditions

The influence of two types of colloids (natural organic matter, NOM), a colloid with high affinity for radionuclides (RN(s)), and hydrophilic synthetic latex (SHL), a colloid with low affinity for RN(s) on the transfer of (60)Co and (85)Sr in a silica sand column was studied under different physicochemical conditions: pH (4.9), ionic strength (10(-3) M and 10(-2) M), concentration of colloids (100 mg l(-1), 10 mg l(-1)), flow velocity (12.4 cm h(-1) and 3.7 cm h(-1)), water saturation of the column (100% and 70%). In the absence of colloids, the transfer of (60)Co and (85)Sr was retarded compared to the transfer of the conservative tracer. In the presence of colloids and according to the specific physicochemical conditions, an acceleration or retardation of (60)Co and (85)Sr transfer was observed compared to their transfer in the absence of colloids. Our results evidenced that any colloids even with low reactivity could significantly modify the RN transfer. However, the extent to which the transfer was influenced differs according to the colloid type; the NOM exhibiting higher impact than SHL. Batch experiments helped in interpreting of the interactions between the colloids, RN(s) and solid phase observed in column.     

Natural organic matter (NOM) in roof runoff and its impact on the Fe0 treatment system of dissolved metals

The present work investigates the impacts and mechanisms associated with natural organic matter (NOM) in the Fe0 treatment system of Cu2+ and Zn2+ under roof runoff conditions. The NOM in runoff waters was characterized using XAD-4/8 adsorption resins, copper complexation, acidic capacity and liquid chromatography with online carbon detection. Batch kinetic experiments and flow-through configurations were performed and the results of metal removal were elucidated taking into account the characteristics of NOM. Based on the findings, it is shown that NOM influences the removal of metals through several complex pathways. At an un-favored condition for adsorption of metals, i.e., on iron corrosion products, at pH相似文献   

Transport of anthracene and benz(a)anthracene through iron-quartz and three aquifer materials in laboratory columns

In groundwater systems, dissolved natural organic matter (NOM) can influence the mobility of organic contaminants by altering the contaminant behavior in water and solid phases. The transport of anthracene and benz(a)anthracene (B(a)A) was studied in the presence and absence of NOM and/or soil organic matter (SOM) in column experiments. The results show that sorption are related to the properties of polycyclic aromatic hydrocarbons (PAHs), NOM and SOM. In the Fe-quartz media, the amount of NOM (20 mg/l) in solution had a little effect on increasing the apparent solubility of anthracene and countering increased anthracene sorption. In the natural (Bemidji) soil, Suwannee river fulvic acid (SRFA, 20 mg/l) and Suwannee river humic acid (SRHA) in water did not compete with SOM for anthracene, indicating that SOM has higher partition efficiency for anthracene. It was also observed that slow diffusion through an organic phase apparently caused most of the observed tailing in column breakthrough curves (BTCs). Even though the fOC of washed Bemidji sediment was very low, the transport of B(a)A was retarded significantly, however, and the transport of B(a)A was shown to be facilitated by dissolved NOM.     

Sorption and desorption hysteresis of organic contaminants by kerogen in a sandy aquifer material

Sorption and desorption hysteresis of 1,2-dichlorobenzene, 1,3,5-trichlorobenzene, naphthalene, and phenanthrene were investigated for the Borden aquifer material with total organic carbon of 0.021% and the isolated natural organic matter (NOM). The isolated NOM is a kerogen type of organic matter with relatively low maturation degree and contained many different types of organic matters including vitrinite particles. The modified Freundlich sorption capacities (logK^′_f and logK^′_foc) are very close for the sorption of the four solutes by the isolated NOM and the original sand, respectively. Isotherm non-linearity (n value) and hysteric behaviors are related to solute molecular properties (e.g. K_ow and molecular size). Kerogen encapsulated by inorganic matrices in the original aquifer may not be accessed fully by solutes. The larger the hydrophobic organic chemical (HOC) (hydrophobic organic contaminant) molecule is, the lower accessibility of the HOC to kerogen. This study disputes widely held hypothesis that sorption to mineral surfaces may play a major role in the overall sorption by low TOC (e.g. 0.1% by mass) geomaterials such as Borden sand. It also demonstrates the importance of the condensed NOM domain, even at very low contents, in the sorption and desorption hysteresis of HOCs in groundwater systems.     

Effects of surface coatings on electrochemical properties and contaminant sorption of clay minerals

Surface charges play a major role in determining the interactions of contaminants with soils. The most important sources of soil charges are clay mineral colloids, whose electrochemical properties are usually modified by metal-oxides and organic matter in natural environments. In this study, effects of coatings of organic matter and Fe- and Al-oxides on a series of electrochemical properties and heavy metal sorption of three clay minerals (kaolinite, montmorillonite and illite) predominant in natural soils were investigated using batch techniques. The results indicate that the coatings increased the specific surface area of the clay minerals, except for the Al-oxide coated montmorillonite and organic matter coated 2:1 clay minerals. The sesquioxide coatings increased amount of positive charges but decreased negative charges. This causes great reduction of the negative potential on the clay surfaces, shift of the zero point of charge to a higher pH, and promotion of fluoride sorption due to presence of more OH- and OH2 on the oxide surfaces than on the clay surfaces. In contrast, the organic coating significantly increased the negativity of surface charges, and thus the zero point of charge and zeta-potential of the clays dropped down. The organic coating also induced a reduction of fluoride sorption on the clays. With respect to the sorption of lead and cadmium, the sesquioxide coatings produced insignificant effects. The experiments of lead/cadmium competitive sorption show that on both the oxide-coated surface and the original clay surface there exist different types of sites, each of which preferentially binds with a heavy metal.     

Fluorescence spectroscopic studies of natural organic matter fractions

Because of the well-known molecular complexity and heterogeneity of natural organic matter (NOM), an aquatic bulk NOM was fractionated into well-defined polyphenolic-rich and carbohydrate-rich subfractions. These fractions were systematically characterized by fluorescence emission, three dimensional excitation-emission matrices, and synchronous-scan excitation spectroscopy in comparison with those of the reference International Humic Substances Society soil humic acid and Suwannee River fulvic acid. Results indicate that fluorescence spectroscopy can be useful to qualitatively differentiate not only NOM compounds from varying origins but also NOM subcomponents with varying compositions and functional properties. The polyphenolic-rich NOM-PP fraction exhibited a much more intense fluorescence and a red shift of peak position in comparison with the carbohydrate-rich NOM-CH fraction. Results also indicate that synchronous excitation spectra were able to provide improved peak resolution and structural signatures such as peak positioning, shift, and intensity among various NOM components as compared with those of the emission and excitation spectra. In particular, the synchronous spectral peak intensity and its red shift in the region of about 450-480 nm may be used to indicate the presence or absence of high molecular weight and polycondensed humic organic components, or the multicomponent nature of NOM or NOM subcomponents.     

Transformation of effluent organic matter during subsurface wetland treatment in the Sonoran Desert

The fate of dissolved organic matter (DOM) during subsurface wetland treatment of wastewater effluent in a hot, semi-arid environment was examined. The study objectives were to (1) discern changes in the character of dissolved organics as consequence of wetland treatment (2) establish the nature of wetland-derived organic matter, and (3) investigate the impact of wetland treatment on the formation potential of trihalomethanes (THMs). Subsurface wetland treatment produced little change in DOM polarity (hydrophobic-hydrophilic) distribution. Biodegradation of labile effluent organic matter (EfOM) and internal loading of wetland-derived natural organic matter (NOM) together produced only minor changes in the distribution of carbon moieties in hydrophobic acid (HPO-A) and transphilic acid (TPI-A) isolates of wetland effluent. Aliphatic carbon decreased as a percentage of total carbon during wetland treatment. The ratio of atomic C:N in wetland-derived NOM suggests that its character is determined by microbial activity. Formation of THMs upon chlorination of HPO-A and TPI-A isolates increased as a consequence of wetland treatment. Wetland-derived NOM was more reactive in forming THMs and less biodegradable than EfOM. For both HPO-A and TPI-A fractions, relationships between biodegradability and THM formation potential were similar among EfOM and NOM isolates; the less biodegradable isolates exhibited greater THM formation potential.     

An overview of the methods used in the characterisation of natural organic matter (NOM) in relation to drinking water treatment

Natural organic matter (NOM) is found in all surface, ground and soil waters. During recent decades, reports worldwide show a continuing increase in the color and NOM of the surface water, which has an adverse affect on drinking water purification. For several practical and hygienic reasons, the presence of NOM is undesirable in drinking water. Various technologies have been proposed for NOM removal with varying degrees of success. The properties and amount of NOM, however, can significantly affect the process efficiency. In order to improve and optimise these processes, the characterisation and quantification of NOM at different purification and treatment processes stages is important. It is also important to be able to understand and predict the reactivity of NOM or its fractions in different steps of the treatment. Methods used in the characterisation of NOM include resin adsorption, size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) spectroscopy, and fluorescence spectroscopy. The amount of NOM in water has been predicted with parameters including UV-Vis, total organic carbon (TOC), and specific UV-absorbance (SUVA). Recently, methods by which NOM structures can be more precisely determined have been developed; pyrolysis gas chromatography-mass spectrometry (Py-GC-MS), multidimensional NMR techniques, and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The present review focuses on the methods used for characterisation and quantification of NOM in relation to drinking water treatment.     

Ligninase-mediated transformation of 4,4′-dibromodiphenyl ether (BDE 15)

The structurally related hydroxylated polybrominated diphenyl ether (PBDE) like hydroxylated 4,4′-dibromodiphenyl ether widely occur in precipitation, surface water, and biotic media. The origins of hydroxylated PBDEs (OH-PBDEs) are of particular interest due to their greater toxic potencies than the corresponding PBDEs. We studied the transformation behavior and products of 4,4′-dibromodiphenyl ether (BDE 15) mediated by lignin peroxidase (LiP), an extracellular enzyme that is produced by certain white rot fungus and is widely present in the natural environment. We found that BDE 15 can be effectively transformed through the reaction mediated by LiP, and two different mono-OH-dibromodiphenyl ethers were identified by using gas chromatography–mass spectrometry (GC-MS) and GC-MS/MS. In particular, we compared the reaction behavior for systems variously containing natural organic matter (NOM) and/or veratryl alcohol (VA), a metabolite that certain fungus produces along with LiP in nature. It was found that the VA’s enhancement effect on LiP performance was impaired by the presence of NOM. The findings in this study provide useful information for better understanding the origins of OH-PBDEs found in the environment.     

Sorption of phenanthrene by nanosized alumina coated with sequentially extracted humic acids

Background, aim, and scope  

Sorption of hydrophobic organic compounds (HOCs) to natural organic matter (NOM) is an important process that affects the transport, transformation, bioavailability, and fate of HOCs in the environment. Manufactured nanoparticles (NPs) such as nano-oxides will inevitably enter the environment in the processes of their production, transfer, and use and could be coated by the ubiquitous NOM. Thus, sorption of HOCs to NOM in the environment could be affected by the NP interactions with NOM. Furthermore, the toxicity of nano-oxides could be increased due to the adsorbed HOCs. Therefore, sorption of phenanthrene by nano-Al₂O₃ coated with humic acid (HA) was examined in this study to explore the possible effect of nanoparticles (NPs) on the environmental behavior of HOCs and the potential environmental and health risks of NPs.     

Enhanced coagulation with polyaluminum chlorides: role of pH/alkalinity and speciation

Enhanced coagulation is considered to be among the best available techniques (BAT) for disinfection by-product (DBP) precursor removal in water treatment. Improving existing understanding requires further consideration of nuances of chemical speciation relative to source water chemistry. In this paper, the effect of alkalinity/pH and speciation on inorganic polymer flocculants, polyaluminum chlorides (PACls) for enhanced particle and natural organic matter (NOM) removal was investigated. Three kinds of well-characterized typical source waters in China with low, moderate, and high alkalinity were selected. Performance of coagulants is controlled not only by preformed species but also by those formed in situ. At neutral and basic pH values, PACls with higher basicity (ratio of OH(-)/Al), which have more stable preformed Alb (the rapid reacted species as in ferron assay), are more efficient for turbidity and NOM removal. At slightly acidic pH, PACls with lower basicity are more efficient since more Alb can be formed in situ. Optimal NOM removal was achieved at pH 5.5-6.5 for all PACls. Basicity, speciation, and dosage of coagulant should be optimized based on raw water alkalinity to enhance the removal efficiency of NOM.     

壳聚糖对地表水中污染物的净化作用

综述了壳聚糖絮凝剂对地表水中悬浮物、天然有机物(NOM)、人工合成有机物(SOCs)、藻类的去除和对细菌的抑制及残留铝的削减作用。壳聚糖在地表水净化中具有一定的应用价值。     

The fate and importance of organics in drinking water treatment: a review

In the pioneer days, the main driving forces for research of organics in drinking water treatment (DWT) were human health risks and optimisation of technology. The focus was on natural organic matter (NOM) structure, disinfection by-products (DBPs) formation, NOM removal by means of coagulation, adsorption, and oxidation, and development of the most efficient water treatment trains. Surprisingly, after decades of research, rapid development of analytical techniques and progress in risk assessment, the same driving forces are still in the limelight — although the topics have changed slightly. The attention switched from trihalomethanes to a new generation of DBPs. The definition of hydrophilic/hydrophobic NOM depends on the technique used for characterisation. It has become evident that numerous organic compounds can threaten water supply sources. Some of them had been ignored or overlooked in the past, but have recently been detected by advanced analytical tools even in drinking water. Prioritisation becomes priority per se. As far as processes are concerned, mainstream research has been following three lines: fouling mechanisms, application of hybrid processes and interactions between synthetic organic chemicals, other water constituents and materials used in DWT. Significant development has been made in membrane technology. This paper presents a broad overview of the recent organics research. Although the state-of-the-art technologies seem to have an answer to each and every question raised, it is still necessary to deal with specific problems on a case-by-case basis mainly due to the unique nature of NOM and different xenobiotics that may appear in various types of waters. In the end, human health risk, which derives from the presence/absence of organics, is only the tip of the iceberg — underneath lies a whole new universe — the socio-economic aspect of water treatment and quality that deserves much more attention.     

Effect of humic acids on physicochemical property and Cd(II) sorption of multiwalled carbon nanotubes

Carbon nanotubes (CNTs), as a type of superior adsorbents for both organic and inorganic contaminants, are increasingly introduced into the environment. Ubiquitous natural organic matter (NOM) would coat on the released CNTs and change their physicochemical properties and sorption of contaminants. The effects of four sequentially extracted humic acids (HAs, as a model NOM) from a peat soil on the physicochemical properties and Cd(II) sorption of three multiwalled CNTs (MWNTs) with different surface areas were investigated. The MWNTs as purchased with very few oxygen-containing functional groups had relatively low sorption capacities (0.93–1.49 mg g⁻¹) for Cd(II) and the sorption capacity increased with increasing surface area of the MWNTs. Surface-coating with the HAs lowered surface areas of the MWNTs but greatly increased their sorption capacities (5.42–18.4 mg g⁻¹). The MWNT-bound HAs introduced oxygen-containing functional groups and negative charges to the MWNT surfaces, which could thus increase the apparent sorption of Cd(II) through chemical complexation and electrostatic attraction, respectively. The later-extracted HAs with lower polarity were more favorable for the surface-coating but increased less Cd(II) sorption by the MWNTs. The results are expected to shed light on understanding the underlying mechanism of the effect of NOM on the sorption of heavy metal ions by CNTs.     

Spectroscopic characterization of the structural and functional properties of natural organic matter fractions

Natural organic matter (NOM) is known to be complex in nature with varying structural and functional characteristics. In this study, an aquatic NOM was fractionated into the polyphenolic-rich (NOM-PP) and the carbohydrate-rich (NOM-CH) fractions in an attempt to better characterize their chemical and structural properties along with a reference soil humic acid (SHA). Various spectroscopic techniques were employed for the study, including ultraviolet-visible (UV/Vis). 13C-nuclear magnetic resonance, Fourier-transform infrared, fluorescence, and electron paramagnetic resonance spectroscopies. Results indicate that the relative abundance of aromatic C=C and methoxyl (-OCH3) functional groups are in the order of SHA > NOM-PP > NOM-CH. However, the aquatic NOM-PP and NOM-CH fractions are characterized by high contents of carboxylic and alcoholic functional groups relative to the SHA. In particular, the NOM-PP fraction appears to contain more phenolic and ketonic functional groups than the NOM-CH and SHA fractions, and it gives a strong fluorescence and high paramagnetic spin count. On the other hand, the NOM-CH fraction possesses a relatively low amount of carbon but a high amount of oxygen or oxygen-containing structural features, such as carbohydrate-OH and carboxylic groups, and shows the least fluorescence intensity and paramagnetic spin counts. Results of these spectroscopic studies confirm the heterogeneous nature of NOM, and point out the importance of isolation and improved characterization of various NOM subcomponents in order to better understand the behavior and roles of NOM in the natural environment.