Gravity-driven membrane filtration with compact second-life modules daily backwashed: An alternative to conventional ultrafiltration for centralized facilities.

Gravity-driven membrane (GDM) filtration is a strategic alternative to conventional ultrafiltration (UF) for the resilient production of drinking water via ultrafiltration when resources become scarce, given the low dependency on energy and chemicals, and longer membrane lifetime. Implementation at large scale requires the use of compact and low-cost membrane modules with high biopolymer removal capacity. We therefore evaluated (1) to what extent stable flux can be obtained with compact membrane modules, i.e., inside-out hollow fiber membranes, and frequent gravity-driven backwash, (2) whether we can reduce membrane expenses by effectively utilizing second-life UF modules, i.e., modules that have been discarded by treatment plant operators because they are no longer under warranty, (3) if biopolymer removal could be maintained when applying a frequent backwash and with second-life modules and (4) which GDM filtration scenarios are economically viable compared to conventional UF, when considering the influence of new or second-life modules, membrane lifetime, stable flux value and energy pricing. Our findings showed that it was possible to maintain stable fluxes around 10 L/m2/h with both new and second-life modules for 142 days, but a daily gravity-driven backwash was necessary and sufficient to compensate the continuous flux drop observed with compact modules. In addition, the backwash did not affect the biopolymer removal. Costs calculations revealed two significant findings: (1) using second-life modules made GDM filtration membrane investment less expensive than conventional UF, despite the higher module requirements for GDM filtration and (2) overall costs of GDM filtration with a gravity-driven backwash were unaffected by energy prices rise, while conventional UF costs rose significantly. The later increased the number of economically viable GDM filtration scenarios, including scenarios with new modules. In summary, we proposed an approach that could make GDM filtration in centralized facilities feasible and increase the range of UF operating conditions to better adapt to increasing environmental and societal constraints.

Controlling the hydraulic resistance of membrane biofilms by engineering biofilm physical structure.

The application of membrane technology for water treatment and reuse is hampered by the development of a microbial biofilm. Biofilm growth in micro-and ultrafiltration (MF/UF) membrane modules, on both the membrane surface and feed spacer, can form a secondary membrane and exert resistance to permeation and crossflow, increasing energy demand and decreasing permeate quantity and quality. In recent years, exhaustive efforts were made to understand the chemical, structural and hydraulic characteristics of membrane biofilms. In this review, we critically assess which specific structural features of membrane biofilms exert resistance to forced water passage in MF/UF membranes systems applied to water and wastewater treatment, and how biofilm physical structure can be engineered by process operation to impose less hydraulic resistance ("below-the-pain threshold"). Counter-intuitively, biofilms with greater thickness do not always cause a higher hydraulic resistance than thinner biofilms. Dense biofilms, however, had consistently higher hydraulic resistances compared to less dense biofilms. The mechanism by which density exerts hydraulic resistance is reported in the literature to be dependant on the biofilms' internal packing structure and EPS chemical composition (e.g., porosity, polymer concentration). Current reports of internal porosity in membrane biofilms are not supported by adequate experimental evidence or by a reliable methodology, limiting a unified understanding of biofilm internal structure. Identifying the dependency of hydraulic resistance on biofilm density invites efforts to control the hydraulic resistance of membrane biofilms by engineering internal biofilm structure. Regulation of biofilm internal structure is possible by alteration of key determinants such as feed water nutrient composition/concentration, hydraulic shear stress and resistance and can engineer biofilm structural development to decrease density and therein hydraulic resistance. Future efforts should seek to determine the extent to which the concept of "biofilm engineering" can be extended to other biofilm parameters such as mechanical stability and the implication for biofilm control/removal in engineered water systems (e.g., pipelines and/or, cooling towers) susceptible to biofouling.

Integrating granular activated carbon (GAC) to gravity-driven membrane (GDM) to improve its flux stabilization: Respective roles of adsorption and biodegradation by GAC.

As a low-maintenance and cost-effective process, gravity-driven membrane (GDM) filtration is a promising alternative for decentralized drinking water supply, while the low flux impedes its extensive application. In order to address such issue, an integrated process consisting of granular activated carbon (GAC) layer and GDM was developed. The performance of virgin (fresh GAC) or preloaded GAC (saturated GAC) was compared. Flux stabilization was observed both in the fresh and saturated GAC/GDM process during long-term filtration and their stable fluxes were both improved by approximately 50% relative to the GDM control. Moreover, integrating GAC with GDM contributed to efficient removals for dissolved organic compounds (DOC), assimilable organic carbon (AOC) and low molecular weight substances both in fresh and saturated GAC/GDM filtration. Compared to GDM control, coupling GAC to GDM could significantly reduce the concentrations of extracellular polymeric substances (EPS) and total cell counts (TCC) within the biofouling layer, and engineer highly heterogeneous structures of biofouling layer on the membrane surface. In the fresh GAC/GDM process, the improved flux obtained was mainly related to less coverage of biofouling layer and lower EPS concentrations due to efficient removals of membrane foulants by GAC adsorption. The achieved higher stable flux can be maintained during long-term filtration (after GAC saturation) owing to the combined effects of EPS reduction and formation of highly heterogeneous structures of biofouling layer in the saturated GAC/GDM system. Overall, the integrated GAC/GDM process can hopefully facilitate improvements both in the stabilized flux and permeate quality, with practical relevance for GDM applications in decentralized drinking water supply.

Competitive co-adsorption of bacteriophage MS2 and natural organic matter onto multiwalled carbon nanotubes.

A leading challenge in drinking water treatment is to remove small-sized viruses from the water in a simple and efficient manner. Multi-walled carbon nanotubes (MWCNT) are new generation adsorbents with previously demonstrated potential as filter media to improve virus removal. This study therefore aimed to evaluate the field applicability of MWCNT-filters for virus removal in water containing natural organic matter (NOM) as co-solute to viruses, using batch equilibrium experiments. Contrary to previous studies, our results showed with MS2 bacteriophages single-solute systems that the affinity of MWCNT for MS2 was low, since after 3 h of equilibration only 4 log10 reduction value (LRV) of MS2 (20 mL at an initial concentration of 106 PFU MS2/mL) were reached. Single solute experiments with Suwannee river NOM (SRNOM) performed with environmentally-relevant concentrations showed MWCNT surface saturation at initial SRNOM concentrations between 10 and 15 mgC/L, for water pH between 5.2 and 8.7. These results suggested that at NOM:virus ratios found in natural waters, the NOM would competitively suppress virus adsorption onto MWCNT, even at low NOM concentrations. We confirmed this expectation with SRNOM-MS2 co-solute experiments, which showed an exponential decrease of the MS2 LRV by MWCNT with an increase in the initial SRNOM concentration. More interestingly, we showed that pre-equilibrating MWCNT with a SRNOM solution at a concentration as low as 0.4 mgC/L resulted in a LRV decrease of 3 for MS2, due to the formation of a negatively charged SRNOM adlayer on the MWCNT surface. Complementary batch experiments with natural NOM-containing waters and competition experiments with SRNOM in the presence of CaCl2 confirmed that the presence of NOM in waters challenges virus removal by MWCNT-filters, irrespective of the concentration and type of NOM and also in the presence of Ca2+. We therefore conclude that MWCNT-filters produced with commercially available pristine MWCNT cannot be considered as a viable technology for drinking water virus removal.

Green Synthesis of Hierarchical Metal-Organic Framework/Wood Functional Composites with Superior Mechanical Properties.

The applicability of advanced composite materials with hierarchical structure that conjugate metal-organic frameworks (MOFs) with macroporous materials is commonly limited by their inferior mechanical properties. Here, a universal green synthesis method for the in situ growth of MOF nanocrystals within wood substrates is introduced. Nucleation sites for different types of MOFs are readily created by a sodium hydroxide treatment, which is demonstrated to be broadly applicable to different wood species. The resulting MOF/wood composite exhibits hierarchical porosity with 130 times larger specific surface area compared to native wood. Assessment of the CO2 adsorption capacity demonstrates the efficient utilization of the MOF loading along with similar adsorption ability to that of pure MOF. Compression and tensile tests reveal superior mechanical properties, which surpass those obtained for polymer substrates. The functionalization strategy offers a stable, sustainable, and scalable platform for the fabrication of multifunctional MOF/wood-derived composites with potential applications in environmental- and energy-related fields.

Dissolved Organic Matter and Associated Trace Metal Dynamics from River to Lake, Under Ice-Covered and Ice-Free Conditions.

The present study investigates the changes in dissolved organic matter (DOM) composition and its influences on trace metal dispersion from the Shuya River (SR) in the Petrozavodsk Bay of Lake Onega during ice-covered and ice-free periods. Humic substances (HS) found in the SR dominated the composition of DOM through the river-bay-lake continuum in both periods. When the bay was ice-covered, both the aromaticity and the size of HS varied in the water column according to a horizontal stratification and decreased in the bay, while under ice-free conditions, they decreased along the river-lake gradient, suggesting in both cases a decrease in the proportion of HS with high aromatic character. These findings were associated with an overall decrease in the proportion of HS components that have the highest molecular masses. The quantification of metal bound to HS revealed that these characteristics were associated with a decrease in the binding capacity of the HS for Fe and Al but not Cu while dispersing in the bay to the lake. Pb was found to bind on HS, but its behavior in the bay could not be related to the HS dispersion nor to the changes in HS properties.

Evaluation of conceptual model and predictors of faecal sludge dewatering performance in Senegal and Tanzania.

Unpredictable dewatering performance is a barrier to the effective management and treatment of faecal sludge. While mechanisms of dewatering in sludges from wastewater treatment are well understood, it is not clear how dewatering of faecal sludge fits into the framework of existing knowledge. We evaluate physical-chemical parameters, including EPS and cations, and demographic (source), environmental (microbial community), and technical factors (residence time) as possible predictors of dewatering performance in faecal sludge, and make comparisons to the existing conceptual model for wastewater sludge. Faecal sludge from public toilets took longer to dewater than sludge from other sources, and had turbid supernatant after settling. Slow dewatering and turbid supernatant corresponded to high EPS and monovalent cation concentrations, conductivity, and pH, but cake solids after dewatering was not correlated with EPS or other factors. Faecal sludges with higher EPS appeared less stabilised than those with lower EPS, potentially a result of inhibition of biological degradation due to high urine concentrations. However, distinct microbial community compositions were also observed in samples with higher and lower EPS concentrations. Higher EPS faecal sludge was comparable in dewatering behaviour and EPS content to anaerobically digested and primary wastewater sludges. However lower EPS faecal sludges had different dewatering behaviour than wastewater sludges and may be governed by different mechanisms.

Enhanced virus filtration in hybrid membranes with MWCNT nanocomposite.

Membrane separation is proved to be a powerful tool for several applications such as wastewater treatment or the elimination of various microorganisms from drinking water. In this study, the efficiency of inorganic composite-based multi-walled carbon nanotube (MWCNT) hybrid membranes was investigated in the removal of MS2 bacteriophages from contaminated water. With this object, multi-walled carbon nanotubes were coated with copper(I) oxide, titanium(IV) oxide and iron(III) oxide nanoparticles, respectively, and their virus removal capability was tested in both batch and flow experiments. Considering the possible pH range of drinking water, the filtration tests were carried out at pH 5.0, 7.5 and 9.0 as well. The extent of MS2 removal strongly depended on the pH values for each composite, which can be due to electrostatic interactions between the membrane and the virus. The most efficient removal (greater than or equal to 99.99%) was obtained with the Cu2O-coated MWCNT membrane in the whole pH range. The fabricated nanocomposites were characterized by X-ray diffraction, specific surface area measurement, dynamic light scattering, zeta potential measurement, Raman spectroscopy, transmission electron microscopy and scanning electron microscopy. This study presents a simple route to design novel and effective nanocomposite-based hybrid membranes for virus removal.

Copper-Coated Cellulose-Based Water Filters for Virus Retention.

Despite recent efforts in modernization of water treatment facilities, the problem of access to healthy drinking water for hundreds of millions of people has still not been solved. A water filter based on Cu-coated nanofibrillated cellulose with controlled porosity was prepared by the "paper-making" method. We have optimized the proper mass and ratio of functionalized and pure nanofibrillated cellulose for the preparation of the filter. MS2 bacteriophages were used to model human pathogenic virions. We tested our filter material in batch experiments and the fixed filters in flow experiments. The fabricated Cu-coated nanofibrillated cellulose filters were characterized by scanning electron microscopy, X-ray diffraction, specific surface area measurement (Brunauer-Emmett-Teller), dynamic light scattering, and inductively coupled plasma mass spectroscopy. Our measurements proved that the fixation of cellulose nanofibers plays a significant role in the degree of virus retention and it greatly enhances the efficiency of the filtration. By using these functionalized water filters, we were able to achieve a virus retention of at least 5 magnitudes (5Log) at three different pH values: 5.0, 7.5, and 9.

Three-dimensional excitation and emission matrix fluorescence (3DEEM) for quick and pseudo-quantitative determination of protein- and humic-like substances in full-scale membrane bioreactor (MBR).

The goal of this study is to help filling the research gaps linked to the on-line application of fluorescence spectroscopy in wastewater treatment and data processing tools suitable for rapid correction and extraction of data contained in three-dimensional fluorescence excitation-emission matrix (3DEEM) for real-time studies. 3DEEM was evaluated for direct quantification of Effluent Organic Matter (EfOM) fractions in full-scale MBR bulk supernatant and permeate samples. Principal Component Analysis (PCA) was used to investigate possible correlations between conventional Lowry and Dubois methods, Liquid Chromatography coupled to Organic Carbon and Organic Nitrogen Detection (LC-OCD-OND) and 3DEEM. 3DEEM data were analyzed using the volume of fluorescence (Φ) parameter from the Fluorescence Regional Integration (FRI) method. Two mathematical correlations were established between LC-OCD-OND and 3DEEM data to quantify protein-like and humic-like substances. These correlations were validated with supplementary data from the initial full-scale MBR, and were checked with samples from other systems (a second full-scale MBR, a full-scale conventional activated sludge (CAS) and a laboratory-scale MBR). While humic-like correlation showed satisfactory prediction for a second full-scale MBR and a CAS system, further studies are required for protein-like estimation in other systems. This new approach offers interesting perspectives for the on-line application of 3DEEM for EfOM quantification (protein-like and humic-like substances), fouling prediction and MBR process control.

Agglomeration of Ag and TiO2 nanoparticles in surface and wastewater: Role of calcium ions and of organic carbon fractions.

This study aims to investigate factors leading to agglomeration of citrate coated silver (AgNP-Cit), polyvinylpyrrolidone coated AgNPPVP and titanium dioxide (TiO2) nanoparticles in surface waters and wastewater. ENPs (1 mg/L) were spiked to unfiltered, filtered, ultrafiltered (<10 kDa and <1 kDa) samples. Z-average particle sizes were measured after 1 h, 1 day and 1 week. AgNP-PVP was stable in all fractions of the samples and kept their original size around 60 nm over 1 week. Agglomeration of AgNP-Cit and TiO2 was positively correlated with Ca(2+) concentration, but dissolved organic carbon concentrations > 2 mg/L contributed to stabilizing these NP. Moreover, agglomeration of AgNP-Cit in the various organic matter fractions showed that high molecular weight organic compounds such as biopolymers provide stabilization in natural water. A generalized scheme for the agglomeration behavior of AgNP-Cit, AgNP-PVP and TiO2 in natural waters was proposed based on their relation with Ca(2+), Mg(2+) and DOC concentration.

Photo-transformation of pedogenic humic acid and consequences for Cd(II), Cu(II) and Pb(II) speciation and bioavailability to green microalga.

Humic substances (HS) play key role in toxic metal binding and protecting aquatic microorganisms from metal-induced stress. Any environmental changes that could alter HS concentration and reactivity can be expected to modify metal complexation and thus affect metal speciation and bioavailability to microalgae. The present study explores the influence of increased solar irradiance on the chemical structures and molecular weight of Elliott soil humic acid (EHA) and the associated consequences for Cd(II), Cu(II) and Pb(II) complexation and intracellular metal content in microalga. The results demonstrate that high radiance doses induce an oxidation of EHA with a formation of low molecular weight acids, an increase of -OH and -COOH group abundance, and a drop in EHA hydrodynamic size and molecular weight. The photo-induced structural changes are accompanied with a release of metal from M-EHA complexes and narrowing their size distribution, which in turn results in an increase of the intracellular Cd, Cu and Pb contents in microalga Chlamydomonas reinhardtii in agreement with the measured free metal ions concentrations.

Quantification and characterization of dissolved organic nitrogen in wastewater effluents by electrodialysis treatment followed by size-exclusion chromatography with nitrogen detection.

Dissolved organic nitrogen (DON) can act as a precursor of nitrogenous disinfection byproducts during oxidative water treatment. Quantification and characterization of DON are still challenging for waters with high concentrations of dissolved inorganic nitrogen (DIN, including ammonia, nitrate and nitrite) relative to total dissolved nitrogen (TDN) due to the cumulative analytical errors of independently measured nitrogen species (i.e., DON = TDN - NO2(-) - NO3(-) - NH4(+)/NH3) and interference of DIN species to TDN quantification. In this study, a novel electrodialysis (ED)-based treatment for selective DIN removal was developed and optimized with respect to type of ion-exchange membrane, sample pH, and ED duration. The optimized ED method was then coupled with size-exclusion chromatography with organic carbon, UV, and nitrogen detection (SEC-OCD-ND) for advanced DON analysis in wastewater effluents. Among the tested ion-exchange membranes, the PC-AR anion- and CMT cation-exchange membranes showed the lowest DOC loss (1-7%) during ED treatment of a wastewater effluent at ambient pH (8.0). A good correlation was found between the decrease of the DIN/TDN ratio and conductivity. Therefore, conductivity has been adopted as a convenient way to determine the optimal duration of the ED treatment. In the pH range of 7.0-8.3, ED treatment of various wastewater effluents with the PC-AR/CMT membranes showed that the relative residual conductivity could be reduced to less than 0.50 (DIN removal >90%; DIN/TDN ratio ≤ 0.60) with lower DOC losses (6%) than the previous dialysis and nanofiltration methods (DOC loss >10%). In addition, the ED method is shorter (0.5 h) than the previous methods (>1-24 h). The relative residual conductivity was further reduced to ≈ 0.20 (DIN removal >95%; DIN/TDN ratio ≤ 0.35) by increasing the ED duration to 0.7 h (DOC loss = 8%) for analysis by SEC-OCD-ND, which provided new information on distribution and ratio of organic carbon and nitrogen in different molecular weight fractions of effluent organic matter.

Characterization of extracellular polymeric substances (EPS) from periphyton using liquid chromatography-organic carbon detection-organic nitrogen detection (LC-OCD-OND).

A protocol was developed to extract, fractionate, and quantitatively analyze periphyton extracellular polymeric substances (EPS), which obtains both information on the molecular weight (M r) distribution and protein and polysaccharide content. The EPS were extracted from freshwater periphyton between July and December 2011. Organic carbon (OC) compounds from different EPS extracts were analyzed using liquid chromatography-organic carbon detection-organic nitrogen detection (LC-OCD-OND), and total protein and polysaccharide content were quantified. Four distinct OC fractions, on the basis of M r, were identified in all extracts, corresponding to high M r biopolymers (≥80-4 kDa), degradation products of humic substances (M r not available), low M r acids (10-0.7 kDa), and small amphiphilic/neutral compounds (3-0.5 kDa). Low C/N ratios (4.3 ± 0.8) were calculated for the biopolymer fractions, which represented 16-38 % of the measured dissolved organic carbon (DOC), indicating a significant presence of high M r proteins in the EPS. Protein and polysaccharide represented the two major components of EPS and, when combined, accounted for the measured DOC in extracts. Differences in specific OC fractions of EPS extracts over the course of the study could be quantified using this method. This study suggests that LC-OCD-OND is a new valuable tool in EPS characterization of periphyton.

Combined nitritation-anammox: advances in understanding process stability.

Efficient nitrogen removal from wastewater containing high concentrations of ammonium but little organic substrate has recently been demonstrated by several full-scale applications of the combined nitritation-anammox process. While the process efficiency is in most cases very good, process instabilities have been observed to result in temporary process failures. In the current study, conditions resulting in instability and strategies to regain efficient operation were evaluated. First, data from full-scale operation is presented, showing a sudden partial loss of activity followed by recovery within less than 1 month. Results from laboratory-scale experiments indicate that these dynamics observed in full scale can be caused by partial inhibition of the ammonia oxidizing bacteria (AOB), while anammox inhibition is a secondary effect due to temporarily reduced O(2) depletion. Complete anammox inhibition is observed at 0.2 mg O(2) · L(-1), resulting in NO(2)(-) accumulation. However, this inhibition of anammox is reversible within minutes after O(2) depletion. Thus, variable AOB activity was identified as the key to reactor stability. With appropriate interpretation of the online NH(4)(+) signal, accumulation of NO(2)(-) can be detected indirectly and used to signal an imbalance of O(2) supply and AOB activity (no suitable online NO(2)(-) electrode is currently available). Second, increased abundance of nitrite-oxidizing bacteria (NOB; competing with anammox for NO(2)(-)) is known as another cause of instability. Based on a comparison of parallel full-scale reactors, it is suggested that an infrequent and short-term increased O(2) supply (e.g., for maintenance of aerators) that exceeds prompt depletion of oxygen by AOB may have caused increased NOB abundance. The volumetric air supply as a proxy for O(2) supply thus needs to be linked to AOB activity. Further, NOB can be washed out of the system during regular operation if the system is operated at a sludge age in the range of 45 days and by controlling the air supply according to the NO(3)(-) concentration in the treated effluent. Early detection of growing NOB abundance while the population is still low can help guide process operation and it is suggested that molecular methods of quantifying NOB abundance should be tested.

Application of an asymmetric flow field flow fractionation multi-detector approach for metallic engineered nanoparticle characterization--prospects and limitations demonstrated on Au nanoparticles.

In this work we discuss about the method development, applicability and limitations of an asymmetric flow field flow fractionation (A4F) system in combination with a multi-detector setup consisting of UV/vis, light scattering, and inductively coupled plasma mass spectrometry (ICPMS). The overall aim was to obtain a size dependent-, element specific-, and quantitative method appropriate for the characterization of metallic engineered nanoparticle (ENP) dispersions. Thus, systematic investigations of crucial method parameters were performed by employing well characterized Au nanoparticles (Au-NPs) as a defined model system. For good separation performance, the A4F flow-, membrane-, and carrier conditions were optimized. To obtain reliable size information, the use of laser light scattering based detectors was evaluated, where an online dynamic light scattering (DLS) detector showed good results for the investigated Au-NP up to a size of 80 nm in hydrodynamic diameter. To adapt large sensitivity differences of the various detectors, as well as to guarantee long term stability and minimum contamination of the mass spectrometer a split-flow concept for coupling ICPMS was evaluated. To test for reliable quantification, the ICPMS signal response of ionic Au standards was compared to that of Au-NP. Using proper stabilization with surfactants, no difference for concentrations of 1-50 µg Au L(-1) in the size range from 5 to 80 nm for citrate stabilized dispersions was observed. However, studies using different A4F channel membranes showed unspecific particle-membrane interaction resulting in retention time shifts and unspecific loss of nanoparticles, depending on the Au-NP system as well as membrane batch and type. Thus, reliable quantification and discrimination of ionic and particular species was performed using ICPMS in combination with ultracentrifugation instead of direct quantification with the A4F multi-detector setup. Figures of merit were obtained, by comparing the results from the multi detector approach outlined above, with results from batch-DLS and transmission electron microscopy (TEM). Furthermore, validation performed with certified NIST Au-NP showed excellent agreement. The developed methods show potential for characterization of other commonly used and important metallic engineered nanoparticles.

Characterization of natural organic matter adsorption in granular activated carbon adsorbers.

The removal of natural organic matter (NOM) from lake water was studied in two pilot-scale adsorbers containing granular activated carbon (GAC) with different physical properties. To study the adsorption behavior of individual NOM fractions as a function of time and adsorber depth, NOM was fractionated by size exclusion chromatography (SEC) into biopolymers, humics, building blocks, and low molecular weight (LMW) organics, and NOM fractions were quantified by both ultraviolet and organic carbon detectors. High molecular weight biopolymers were not retained in the two adsorbers. In contrast, humic substances, building blocks and LMW organics were initially well and irreversibly removed, and their effluent concentrations increased gradually in the outlet of the adsorbers until a pseudo-steady state concentration was reached. Poor removal of biopolymers was likely a result of their comparatively large size that prevented access to the internal pore structure of the GACs. In both GAC adsorbers, adsorbability of the remaining NOM fractions, compared on the basis of partition coefficients, increased with decreasing molecular size, suggesting that increasingly larger portions of the internal GAC surface area could be accessed as the size of NOM decreased. Overall DOC uptake at pseudo-steady state differed between the two tested GACs (18.9 and 28.6 g-C/kg GAC), and the percent difference in DOC uptake closely matched the percent difference in the volume of pores with widths in the 1-50 nm range that was measured for the two fresh GACs. Despite the differences in NOM uptake capacity, individual NOM fractions were removed in similar proportions by the two GACs.

Formation of assimilable organic carbon during oxidation of natural waters with ozone, chlorine dioxide, chlorine, permanganate, and ferrate.

Five oxidants, ozone, chlorine dioxide, chlorine, permanganate, and ferrate were studied with regard to the formation of assimilable organic carbon (AOC) and oxalate in absence and presence of cyanobacteria in lake water matrices. Ozone and ferrate formed significant amounts of AOC, i.e. more than 100 µg/L AOC were formed with 4.6 mg/L ozone and ferrate in water with 3.8 mg/L dissolved organic carbon. In the same water samples chlorine dioxide, chlorine, and permanganate produced no or only limited AOC. When cyanobacterial cells (Aphanizomenon gracile) were added to the water, an AOC increase was detected with ozone, permanganate, and ferrate, probably due to cell lysis. This was confirmed by the increase of extracellular geosmin, a substance found in the selected cyanobacterial cells. AOC formation by chlorine and chlorine dioxide was not affected by the presence of the cells. The formation of oxalate upon oxidation was found to be a linear function of the oxidant consumption for all five oxidants. The following molar yields were measured in three different water matrices based on oxidant consumed: 2.4-4.4% for ozone, 1.0-2.8% for chlorine dioxide and chlorine, 1.1-1.2% for ferrate, and 11-16% for permanganate. Furthermore, oxalate was formed in similar concentrations as trihalomethanes during chlorination (yield ∼ 1% based on chlorine consumed). Oxalate formation kinetics and stoichiometry did not correspond to the AOC formation. Therefore, oxalate cannot be used as a surrogate for AOC formation during oxidative water treatment.

Uptake of Cd(II) and Pb(II) by microalgae in presence of colloidal organic matter from wastewater treatment plant effluents.

The present study addresses the key issue of linking the chemical speciation to the uptake of priority pollutants Cd(II) and Pb(II) in the wastewater treatment plant effluents, with emphasis on the role of the colloidal organic matter (EfOM). Binding of Cd(II) and Pb(II) by EfOM was examined by an ion exchange technique and flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry in parallel to bioassays with green microalga Chlorella kesslerii in ultrafiltrate (<1 kDa) and colloidal isolates (1 kDa to 0.45 mum). The uptake of Cd by C. kesslerii was consistent with the speciation analysis and measured free metal ion concentrations, while Pb uptake was much greater than that expected from the speciation measurement. Better understanding of the differences in the effects of the EfOM on Cd(II) and Pb(II) uptake required to take into account the size dependence of metal binding by EfOM.

Cadmium speciation and accumulation in periphyton in a small stream with dynamic concentration variations.

Accumulation of cadmium in periphyton was investigated under field conditions while Cd concentration and speciation were dynamically varying in a small stream during rain events. Speciation in water was determined in situ by diffusion gradient in thin-films (DGT) and by modeling of complexation with fulvic acids. During the rain events, dissolved Cd concentrations increased from 0.17 nM to 0.27-0.36 nM, and 70-97% were DGT-labile. Cd content in periphyton closely followed Cd concentrations in water, despite higher concentrations of Zn and Mn, and may be controlled by either free or DGT-labile Cd concentrations. Decrease of Cd content in periphyton after the rain events was slower than the decrease of Cd concentration in water. Concentrations of Zn, Mn, Cu, Pb and Fe in periphyton also followed the dynamic variations of metal concentrations in water. Repeated exposure of periphyton to elevated dissolved Cd may lead to Cd accumulation.