Aggregation behavior of TiO2 nanoparticles in municipal effluent: Influence of ionic strengthen and organic compounds.

The influence of ionic strengthen and dissolved organic matter (DOM) on the aggregation of TiO2 nanoparticles (NPs) in municipal effluent was investigated. The results demonstrated that DOM promoted the mobility of NPs in aquatic system by synergism between static repulsion and steric effect, while electrolytes were opposite by charge-neutralization. The physical-chemical characteristics of DOM played the major role on the mobility of NPs. Bovine serum albumin (BSA) showed the strongest enhancement on the mobility of TiO2 NPs. High adsorption of BSA introduced vast negative charges on the TiO2 NPs' surface, leading to static repulsion and neutralizing positive charges of electrolytes in surrounding as well. By contrast, another protein α-amylase retarded the aggregation rate of TiO2 NPs through steric repulsion of the long-chain construction. Humic substances (Fulvic acid and alginate) also reflected the combination of static repulsion and steric effect. However, in the high electrolytes concentration (especially Ca2+), the long-chain aliphatic compounds were prone to form calcium bridge which increased the hydrodynamic diameter of TiO2 aggregates consequently. Sodium dodecylbenzene sulfonate (SDBS) showed low adsorption capacity, while the unabsorbed SDBS retarded the aggregates caused by the changes of pH and electrolytes. These data indicated that decreasing of DOC concentration in aqueous system was important to reduce the mobility and potential risk of NPs in aqueous system.

Biodegradation of phenol, salicylic acid, benzenesulfonic acid, and iomeprol by Pseudomonas fluorescens in the capillary fringe.

Mass transfer and biological transformation phenomena in the capillary fringe were studied using phenol, salicylic acid, benzenesulfonic acid, and the iodinated X-ray contrast agent iomeprol as model organic compounds and the microorganism strain Pseudomonas fluorescens. Three experimental approaches were used: Batch experiments (uniform water saturation and transport by diffusion), in static columns (with a gradient of water saturation and advective transport in the capillaries) and in a flow-through cell (with a gradient of water saturation and transport by horizontal and vertical flow: 2-dimension flow-through microcosm). The reactors employed for the experiments were filled with quartz sand of defined particle size distribution (dp=200...600 µm, porosity ε=0.42). Batch experiments showed that phenol and salicylic acid have a high, whereas benzenesulfonic acid and iomeprol have a quite low potential for biodegradation under aerobic conditions and in a matrix nearly close to water saturation. Batch experiments under anoxic conditions with nitrate as electron acceptor revealed that the biodegradation of the model compounds was lower than under aerobic conditions. Nevertheless, the experiments showed that the moisture content was also responsible for an optimized transport in the liquid phase of a porous medium. Biodegradation in the capillary fringe was found to be influenced by both the moisture content and availability of the dissolved substrate, as seen in static column experiments. The gas-liquid mass transfer of oxygen also played an important role for the biological activity. In static column experiments under aerobic conditions, the highest biodegradation was found in the capillary fringe (e.g. ßt/ß0 (phenol)=0 after t=6 d) relative to the zone below the water table and unsaturated zone. The highest biodegradation occurred in the flow-through cell experiment where the height of the capillary fringe was largest.

Mass spectrometric screening and identification of acidic metabolites in fulvic acid fractions of contaminated groundwater.

The anaerobic microbial degradation of aromatic and heterocyclic compounds is a prevalent process in contaminated groundwater systems. The introduction of functional groups into the contaminant molecules often results in aromatic and heterocyclic and succinic acids. These metabolites can be used as indicators for prevailing degradation processes. Therefore, there is a strong interest in developing analytical methods for screening and identification of these metabolites. In this study, neutral loss scans (NLS) by liquid chromatography-electrospray ionization/tandem mass spectrometry with losses of CO2 (NL ∆m/z = 44) and C2H4(CO2)2 (NL ∆m/z = 116) were applied for the first time successfully to screen selectively for acidic and succinic metabolites of aromatic and heterocyclic contaminants in two fulvic acid fractions from a contaminated site and a downstream region of a tar oil-polluted groundwater. Identification of these preselected signals was performed by high-resolution mass spectrometry with a liquid chromatography-electrospray ionization quadrupole time-of-flight mass spectrometry instrument. High-resolution mass and mass fragmentation data were then compared with a list of known metabolites from a literature search or matched with chemical databases supported with in silico fragmentation. Based on authentic analytical standards, several compounds from NLS were identified (e.g., 4-hydroxy-3-methylbenzoic acid, benzylsuccinic acid, naphthyl-2-methylsuccinic acid, 2-carboxyindane, and 2-carboxybenzothiophene) and tentatively identified (e.g., benzofuranmethylsuccinic acid and dihydrocarboxybenzothiophene) as aromatic, phenolic, heterocyclic, and succinic acids. The acidic metabolites were found exclusively in the contaminated region of the aquifer which indicates active biodegradation processes and no relevant occurrence of acidic metabolites in the downstream region.

Evaluation of natural organic matter changes from Lake Hohloh by three-dimensional excitation-emission matrix fluorescence spectroscopy during TiO(2)/UV process.

This study shows the changes of natural organic matter (NOM) from Lake Hohloh, (Black Forest, Germany) during heterogeneous photocatalysis with TiO2 (TiO2/UV). The effect of pH on the adsorption of NOM onto TiO2 in the dark and TiO2/UV degradation of NOM was followed using three-dimensional excitation-emission matrix (EEM) fluorescence. At pH values between 4 and 9, the NOM was adsorbed onto TiO2 in the dark with a greater decrease in the fluorescence intensity and in the spectral shapes, especially under acidic pH conditions. However, at pH = 10 there was not adsorption on NOM which led to a negligible changes the fluorescence intensity. A significant high linear correlation was observed between the DOC adsorption onto TiO2 and the maximum fluorescence intensity. Additionally, the NOM adsorption onto TiO2 and its TiO2/UV degradation shifted the fluorescence maxima toward shorter wavelengths in the EEM contour plots, with a decrease in aromaticity. These changes were accompanied by a substantial decrease in the organically bound halogens adsorbable on activated carbon (AOXFP) and the trihalomethane formation potential (THMFP). Thus, the decrease in maximum fluorescence intensity can be used as an indicator of AOXFP and TTHMFP removal efficiency. Therefore, fluorescence spectroscopy is a robust analytical technique for evaluate TiO2/UV removal of NOM.

Evaluations of the TiO2/simulated solar UV degradations of XAD fractions of natural organic matter from a bog lake using size-exclusion chromatography.

This work reports on the changes in compositions of humic acids (HAs) and fulvic acids (FAs) during photocatalytic degradation. The HAs and FAs were obtained from the XAD-resin fractionation of natural-organic matter (NOM) from a bog lake (Lake Hohloh, Black Forest, Germany). Degussa P-25 titanium dioxide (TiO2) in a suspension and a solar UV simulator (batch reactor) were used in the experiments. The photocatalytic degradation of the HAs and FAs were monitored using size-exclusion chromatography (SEC) equipped with dissolved organic carbon (DOC) and ultraviolet (UV254) detection (SEC-DOC and SEC-UV254) and UV-Vis spectrophotometry. The evolutions of the photocatalytic degradations of the HA and FA fractions were selective. The photocatalytic degradation started with the degradations of high molecular weight compounds with relatively high UV254 absorbances in the HA and FA fractions to yield low molecular weight compounds showing less specific UV254 absorbances. Observance of the same tendency for the original NOM from Lake Hohloh indicates that these XAD-fractions still having complex compound mixtures. However, the larger molecular weight fractions of the FAs showed higher preferential adsorptions onto TiO2, which caused their faster degradation rates. Furthermore, FAs showed a greater reduction of the total THM formation potential (TTHMFP) and the organic halogen compounds adsorbable on activated carbon formation potential (AOXFP), in comparison with the HAs.

Influence of the pH-value on the photocatalytic disinfection of bacteria with TiO2--explanation by DLVO and XDLVO theory.

A photocatalytic disinfection with P25 TiO(2) was conducted at three pH-values (4, 7 and 10) in NaCl solution (c = 10 mmol L(-1)). Neither the osmotic stress nor solely the pH-value had a significant impact on the survival of the Escherichia coli cells. The cells were more damaged at pH 4 than at pH 7 and 10 in irradiation experiments with TiO(2). The smallest disinfection rates occurred at pH 10. SEM images revealed that the surface of the cells was covered with TiO(2) to a greater extent at pH 4 compared to pH 10. At pH 10, the disinfection rates increased when increasing the ionic strength and changing the NaCl solution to CaCl(2). The results indicate that the disinfection rates depend on the electrostatic interaction between cells and TiO(2). The differences could be qualitatively better explained by the XDLVO theory in comparison to the DLVO theory.

Application of excitation-emission fluorescence matrices and UV/Vis absorption to monitoring the photocatalytic degradation of commercial humic acid.

This study reports the use of excitation-emission matrix (EEM) fluorescence and UV/Vis spectroscopy to monitor the changes in the composition and reactivity of Aldrich humic acids (Aldrich HA) as a model compound for natural organic matter (NOM) during photocatalytic degradation. Degussa P-25 titanium dioxide (TiO(2)) and a solar UV-light simulator (a batch reactor) were used. The photocatalysis shifted the fluorescence maxima of EEMs of Aldrich HA toward shorter wavelengths, which implied that the photocatalytic degradation of commercial Aldrich HA caused the breakdown of high molecular weight components and the formation of lower molecular weight fractions. In addition, the fluorescence intensity of fulvic- and humic-like Aldrich HA presented a strong correlation with dissolved organic carbon (DOC), specific UV absorbance (SUVA) parameters, trihalomethane formation potential (THMFP), and organically bound halogens absorbable on activated carbon formation potential (AOXFP). Fluorescence spectroscopy was shown to be a powerful tool for monitoring of the photocatalytic degradation of HA.

Study of pH effects on the evolution of properties of brown-water natural organic matter as revealed by size-exclusion chromatography during photocatalytic degradation.

This study shows the effect of pH on the photocatalytic degradation of natural organic matter (NOM). The experiments were carried out in batch reactor (a solar UV-light simulator) with Degussa P-25 titanium dioxide (TiO2). The NOM degradation was followed by size-exclusion chromatography for dissolved organic carbon (DOC), ultraviolet absorption and fluorescence-detection (SEC-DOC, SEC-UV254 and SEC-Fl254/450). Changes in pH values affected the adsorption of NOM onto TiO2, but did not affect the photodegradation sequence of NOM. For high or low pH values, the degradation of the NOM preferentially removed the larger molecular size fraction in comparison to the middle and small molecular size fractions, resulting in the relative increase of these smaller fractions. This sequence of NOM degradation leads to the evolution of the formation potential for disinfection by-products (DBPs). Specifically, the trihalomethanes and halogenated organic compounds formation potential (THMF and AOXFP) decreased steadily.

Nanoparticles in aquatic systems.

Nanoparticles (NP) are ubiquitous in environmental and technical aquatic systems. Understanding the role and the fate of NP in these systems is an interdisciplinary challenge requiring innovative experimental, theoretical and analytical approaches and critical reflection of classical concepts. This contribution critically reviews the outstanding properties of NP and the resulting consequences for their behaviour in environmental and technical aquatic systems considering natural NP which are mostly geogenic or biogeogenic, and engineered NP. Owing to the severe lack of data on the occurrence of NP in environmental aquatic systems, it is a key task of researchers to further develop analytical methods for the sensitive detection of NP directly in aqueous samples. There is urgent need for standardisation of analytical methods for detection and characterisation of NP, and for toxicity tests to assess possible adverse effects of NP. In this context, NP reference materials have to be defined as a common fundament for research in this field.

Trichloramine in swimming pools--formation and mass transfer.

Trichloramine is a volatile, irritant compound of penetrating odor, which is found as a disinfection by-product in the air of chlorinated indoor swimming pools from reactions of nitrogenous compounds with chlorine. Acid amides, especially urea, ammonium ions and α-amino acids have been found as most efficient trichloramine precursors at acidic and neutral pH. For urea a relative NCl(3) formation of 96% at pH 2.5 and 76% at pH 7.1 was determined. Even under sub-stoichiometric molar ratios of Cl/N the formation of NCl(3) is favored over mono and dichlorinated products. However, the reaction kinetics of urea with chlorine is slow under conditions relevant for swimming pools. Also the mass transfer of NCl(3) from water to the gas phase which was calculated by the Deacon's boundary layer model could be shown as a relatively slow process. Mass transfer would take 20 h or 5.8 d for a rough or a quiescent surface of the water, respectively. This is much more than a typical turnover rate of 6-8 h of a treatment cycle of a 25 m swimming pool. Therefore processes to remove NCl(3) and its precursors can help to minimize the exposure of bathers.

Interactions and stability of silver nanoparticles in the aqueous phase: Influence of natural organic matter (NOM) and ionic strength.

The rapid development of nanotechnology and the related production and application of nanosized materials such as engineered nanoparticles (ENP) inevitably lead to the emission of these products into environmental systems. So far, little is known about the occurrence and the behaviour of ENP in environmental aquatic systems. In this contribution, the influence of natural organic matter (NOM) and ionic strength on the stability and the interactions of silver nanoparticles (n-Ag) in aqueous suspensions was investigated using UV-vis spectroscopy and asymmetrical flow field-flow fractionation (AF4) coupled with UV-vis detection and mass spectrometry (ICP-MS). n-Ag particles were synthesized by chemical reduction of AgNO3 with NaBH4 in the liquid phase at different NOM concentrations. It could be observed that the destabilization effect of increasing ionic strength on n-Ag suspensions was significantly decreased in the presence of NOM, leading to a more stable n-Ag particle suspension. The results indicate that this behaviour is due to the adsorption of NOM molecules onto the surface of n-Ag particles ("coating") and the resulting steric stabilization of the particle suspension. The application of AF4 coupled with highly sensitive detectors turned out to be a powerful method to follow the aggregation of n-Ag particle suspensions at different physical-chemical conditions and to get meaningful information on their chemical composition and particle size distributions. The method described will also open the door to obtain reliable data on the occurrence and the behaviour of other ENP in environmental aquatic systems.

Effect of selected metal ions on the photocatalytic degradation of bog lake water natural organic matter.

Herein we report the photocatalytic degradation of natural organic matter from a bog lake (Lake Hohloh, Black Forest, Germany) in the presence of 0, 5, and 10 µmol L(-1) of added Cu(2+), Mn(2+), Zn(2+) and Fe(3+). The reactions were followed by size exclusion chromatography with organic carbon detection (SEC-DOC) and by measurements of low molecular weight organic acids. Addition of Cu(2+) had the largest effect of all four studied metals, leading to a retardation in the molecular size changes in NOM: degradation of the larger molecular weight fraction was inhibited leading to reduced production of smaller molecular weight metabolites. Similarly, addition of Cu(2+) reduced the production of formic and oxalic acids, and reduced the bioavailability of the partially degraded NOM.

Metabolites indicate hot spots of biodegradation and biogeochemical gradients in a high-resolution monitoring well.

Anaerobic degradation processes play an important role in contaminated aquifers. To indicate active biodegradation processes signature metabolites can be used. In this study field samples from a high-resolution multilevel well in a tar oil-contaminated, anoxic aquifer were analyzed for metabolites by liquid chromatography-tandem mass spectrometry and time-of-flight mass spectrometry. In addition to already known specific degradation products of toluene, xylenes, and naphthalenes, the seldom reported degradation products benzothiophenemethylsuccinic acid (BTMS), benzofuranmethylsuccinic acid (BFMS), methylnaphthyl-2-methylsuccinic acid (MNMS), and acenaphthene-5-carboxylic acid (AC) could be identified (BFMS, AC) and tentatively identified (BTMS, MNMS). The occurrence of BTMS and BFMS clearly show that the fumarate addition pathway, known for toluene and methylnaphthalene, is also important for the anaerobic degradation of heterocyclic contaminants in aquifers. The molar concentration ratios of metabolites and their related parent compounds differ over a wide range which shows that there is no simple and consistent quantitative relation. However, generally higher ratios were found for the more recalcitrant compounds, which are putatively cometabolically degraded (e.g., 2-carboxybenzothiophene and acenaphthene-5-carboxylic acid), indicating an accumulation of these metabolites. Vertical concentration profiles of benzylsuccinic acid (BS) and methyl-benzylsuccinic acid (MBS) showed distinct peaks at the fringes of the toluene and xylene plume indicating hot spots of biodegradation activity and supporting the plume fringe concept. However, there are some compounds which show a different vertical distribution with the most prominent concentrations where also the precursor compounds peaked.

The hybrid process TiO(2)/PAC: performance of membrane filtration.

In investigations concerning the photocatalytic degradation by TiO(2) usually filter discs with a pore size of 0.22 mum and 0.45 mum are used for the removal of photocatalyst particles in aqueous suspensions. In this study the effective rejection of suspended particles by microfiltration in different types of membrane modules and with different membrane materials was investigated. Furthermore, Powdered Activated Carbon (PAC), which can be used to gain an increase in photocatalytic degradation rates, was investigated concerning its influence on the membrane performance. It is shown that by membrane filtration with a pore size above 0.1 mum, irrespective of the experimental conditions, no complete removal can be achieved. However, UV irradiation was found to improve the removal efficiency for all types of tested membrane materials. The addition of PAC also led to a higher performance of membrane filtration with regard to particle rejection. In long-term experiments with a hollow fibre membrane module in the presence of PAC a five-fold decrease of TiO(2) particles in the permeate could be proven. Besides, it was shown that added PAC can shield the membrane regarding the abrasivity of TiO(2), which could otherwise lead to the destruction of the membrane. Therewith PAC exhibits another crucial advantage besides its synergetic effect in photodegradation.

Influence of the zeta potential on the sorption and toxicity of iron oxide nanoparticles on S. cerevisiae and E. coli.

The influence of the zeta potential on the sorption between microorganisms (Saccharomyces cerevisiae and Escherichia coli) and iron oxide nanoparticles is demonstrated in a model salt solution at two different pH-values. There was only a 1% survival rate of E. coli (4.5 x 10(7)cells/mL) in the presence of 24 mg/L nanoparticulate iron oxide at pH 4. S. cerevisiae were less affected by the presence of the nanoparticulate iron oxide. The extent of iron oxide nanoparticle coverage on the surface of the microorganisms appears to be related to electrostatic interaction forces. Furthermore, the toxic effect of the nanoparticle concentration follows the sorption isotherm for E. coli. Based on the resulting hydrodynamic size distributions in the supernatant after sorption experiments, it could be shown that predominantly smaller particle aggregates oxide were sorbed onto E. coli. This was evident by a shift in the particle size distribution towards a larger mean particle size. The effect was observed to a lower extent for S. cerevisiae. The extent of iron oxide nanoparticle sorption on E. coli quickly reached a maximum and remained constant during a 24 h period compared to S. cerevisiae where sorption increased over time.

Photocatalytic degradation of clofibric acid, carbamazepine and iomeprol using conglomerated TiO2 and activated carbon in aqueous suspension.

The combination of powdered activated carbon (PAC) and TiO(2) has been tested for synergistic/antagonistic effects in the photocatalytic degradation of carbamazepine, clofibric acid and iomeprol. Synergistic effects are thought to be caused by rapid adsorption on the PAC surface followed by diffusion to the TiO(2) surface and photocatalytic degradation. The Freundlich constant K(F) was used for comparing the sorption properties of the three substances and it was found that K(F) for clofibric acid was 3 times lower than for carbamazepine and iomeprol, regardless of the kind of PAC used. A PAC with a distinct tendency to form conglomerates was selected so that a high percentage of the PAC surface was in direct proximity to the TiO(2) surface. The photocatalytic degradation of the pharmaceutically active compounds studied followed pseudo-first order kinetics. Synergistic effects only occurred for clofibric acid (factor 1.5) and an inverse relationship between adsorption affinity and synergistic effects was found. High affinity of the target substances to the PAC surface seemed to be counterproductive for the photocatalytic degradation.

Nitrifying microorganisms in fixed-bed biofilm reactors fed with different nitrite and ammonia concentrations.

Nitrifying bacteria and archaea were fed in fixed-bed biofilm reactors with different nitrite and ammonia concentrations in synthetic and real wastewater. During high nitrite concentrations (rho(NO(2)(-))=5-10mg/L), an increase in the abundance of Nitrobacter species was detected with fluorescence in situ hybridization (FISH), while Nitrospira species disappeared to a large extent. During high ammonia concentrations (rho(NH(4)(+))=60-80 mg/L), a slight increase in ammonia-oxidizing bacteria was obtained, while the abundance of archaebacteria remained unchanged. Lab-scale reactors showed a similar nitrifying microbial population as reactors fed with real wastewater. However, increased abundances of Nitrospira species as observed in wastewater reactors and in the wastewater trickling filters could not be found in the laboratory reactors.

Use of fluorescence fingerprints for the estimation of bloom formation and toxin production of Microcystis aeruginosa.

The development of methods facilitating the detection of cyanobacterial blooms in drinking water reservoirs at an early stage is of great importance. Fluorescence spectroscopy could meet these requirements. The study contains the examination of possible correlations between the different maxima of a fluorescence excitation-emission matrix and the amount of produced and excreted toxins of a lab culture of Microcystis aeruginosa at different stages of growth. Various fluorescence signals (protein-like and humic-like substances, pigments) are suited for an estimation of cell density and actual intra- and extracellular toxin concentration. One signal at 315nm/396nm presumably originating from protein-like substances might be useful as a tool for the prediction of increasing cyanobacterial toxin concentrations. As the measurement of fluorescence matrices is still time consuming, synchronous scans with Deltalambda=80nm were tested as a potential alternative. They accurately depict the course of protein-like and humic-like fluorescence during the different stages of growth although especially the latter one is not captured at its maximum. However, due to insufficient separation of chlorophyll a and phycocyanin, the image of the matrix maxima by synchronous scans with Deltalambda=80nm can only be used with minor restrictions. Nevertheless, fluorescence spectroscopy seems to be a powerful tool for the evaluation of cyanobacterial blooms.

The concentration of polysaccharides and proteins in EPS of Pseudomonas putida and Aureobasidum pullulans as revealed by 13C CPMAS NMR spectroscopy.

Extracellular polymeric substances were extracted from the bacterial strain Pseudomonas putida and the fungal species Aureobasidium pullulans using three different methods (formaldehyde-NaOH, ethylenediaminetetraacetic acid (EDTA) and cation-exchange-resin). The composition of the extracellular polymeric substances (EPS) was analysed by biochemical and high-resolution solid state 13C nuclear magnetic resonance (NMR) spectroscopic methods. The EPS yield was strongly dependent on the extraction method, with the formaldehyde-NaOH method showing the best extraction efficiency. The NMR method revealed that when using the EDTA extraction method, about 40% of the EDTA accumulated in the EPS and that was responsible for the apparent high extraction yields. EPS protein content determined by the NMR method was up to 30% higher than the protein content determined using the biochemical (Lowry) method for P. putida and for A. pullulans. The average protein carbon content determined by the NMR method was approximately 70% of the total carbon content. NMR results could be supported by elemental analysis, which showed a high nitrogen content (approximately 10%) in the EPS. The carbohydrate carbon content detected with both methods in the cell aggregates and the EPS was approximately 20% in each. In this study, quantitative 13C cross-polarisation magic angle spinning NMR spectroscopy was conducted on unlabeled cell strains, and EPS and could be used to quantify protein and carbohydrate of different samples.

Electrochemical reduction of the iodinated contrast medium iomeprol: iodine mass balance and identification of transformation products.

Potentiostatic-controlled electrochemical reduction of iomeprol was used to deiodinate iomeprol (IMP), a representative of the iodinated X-ray contrast media. The reduction process was followed by product analysis with liquid chromatography-electrospray ionization-tandem mass spectrometry and ion chromatography-inductively coupled plasma-mass spectrometry. The identification is mainly based on the interpretation of the mass fragmentation. The product analysis showed a rather selective deiodination process with the successive occurrence of IMP-I, IMP-2I, IMP-3I, and a transformation product (TP), respectively. The TP was formed from IMP-3I by a further cleavage of an amide bond and release of a (C=O)CHOH group from the side chain of IMP. The iodine mass balance on the basis of IMP and iodide showed a gap of about 26% at the beginning of the electrolysis process which could be completely closed by taking the intermediates IMP-I and IMP-2I into consideration. This means that the major intermediates and the TPs were considered and that the reduction process is a rather selective one to remove organically bound iodine from X-ray contrast media. An attractive application area would be the electrochemical deiodination of X-ray contrast media in urine of patients or hospital effluents.