Jacqueline Traber

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.

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.

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.

Colloidal organic matter from wastewater treatment plant effluents: Characterization and role in metal distribution

Colloidal organic matter from wastewater treatment plants was characterized and examined with respect to its role in metal distribution by using tangential flow ultrafiltration, liquid chromatography coupled with organic carbon and UV detectors, and an asymmetrical flow field-flow fractionation (AFlFFF) multidetection platform. Results revealed that a humic-like fraction of low aromaticity with an average molar mass ranging from 1600 to 2600Da was the main colloidal component. High molar mass fractions (HMM), with molar mass ranges between 20 and 200kDa, were present in lower proportions. Ag, Cd, Cu, Cr, Mn and Zn were found mainly in the dissolved phase (<0.45microm) and their distribution between colloidal and truly dissolved fractions was strongly influenced by the distribution of dissolved organic carbon. AFlFFF coupled to ICP-MS showed that Ag, Cd, Cu, Cr, Mn and Zn associate to the low molar mass fraction of the colloidal pool, whereas Al, Fe and Pb were equally bound to low and high molar mass fractions.

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.

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.

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.

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.

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.