Henrik Tækker Madsen

Study of degradation intermediates formed during electrochemical oxidation of pesticide residue 2,6-dichlorobenzamide (BAM) at boron doped diamond (BDD) and platinum-iridium anodes

Electrochemical oxidation is a promising technique for degradation of otherwise recalcitrant organic micropollutants in waters. In this study, the applicability of electrochemical oxidation was investigated concerning the degradation of the groundwater pollutant 2,6-dichlorobenzamide (BAM) through the electrochemical oxygen transfer process with two anode materials: Ti/Pt90-Ir10 and boron doped diamond (Si/BDD). Besides the efficiency of the degradation of the main pollutant, it is also of outmost importance to control the formation and fate of stable degradation intermediates. These were investigated quantitatively with HPLC-MS and TOC measurements and qualitatively with a combined HPLC-UV and HPLC-MS protocol. 2,6-Dichlorobenzamide was found to be degraded most efficiently by the BDD cell, which also resulted in significantly lower amounts of intermediates formed during the process. The anodic degradation pathway was found to occur via substitution of hydroxyl groups until ring cleavage leading to carboxylic acids. For the BDD cell, there was a parallel cathodic degradation pathway that occurred via dechlorination. The combination of TOC with the combined HPLC-UV/MS was found to be a powerful method for determining the amount and nature of degradation intermediates.

Membrane Filtration in Water Treatment: Removal of Micropollutants

Abstract Membranes are quickly becoming an increasing important technique in water treatment. They are very versatile and can be used in many applications depending on the specific intrinsic properties of the membrane. In this chapter the focus is on the removal of micropollutants with pressure-driven membranes. Micropollutants offers a significant challenge in traditional water treatment where they are unaffected by most techniques, and membrane treatment offers an interesting alternative to existing technologies such as activated carbon, especially if they are integrated with other techniques such as advanced oxidation processes. The chapter gives a general introduction to membrane technology and theory in which models that can be used to describe the rejection of micropollutants. In the end of the chapter the potential of integrating membranes with advanced oxidation processes is investigated and a review of research on membranes for micropollutant removal is presented together with examples of already existing applications of membranes.

Study of degradation intermediates formed during electrochemical oxidation of pesticide residue 2,6-dichlorobenzamide (BAM) in chloride medium at boron doped diamond (BDD) and platinum anodes

For electrochemical oxidation to become applicable in water treatment outside of laboratories, a number of challenges must be elucidated. One is the formation and fate of degradation intermediates of targeted organics. In this study the degradation of the pesticide residue 2,6-dichlorobenzamide, an important groundwater pollutant, was investigated in a chloride rich solution with the purpose of studying the effect of active chlorine on the degradation pathway. To study the relative importance of the anodic oxidation and active chlorine oxidation in the bulk solution, a non-active BDD and an active Pt anode were compared. Also, the effect of the active chlorine oxidation on the total amount of degradation intermediates was investigated. We found that for 2,6-dichlorobenzamide, active chlorine oxidation was determining for the initial step of the degradation, and therefore yielded a completely different set of degradation intermediates compared to an inert electrolyte. For the Pt anode, the further degradation of the intermediates was also largely dependent on active chlorine oxidation, while for the BDD anode anodic oxidation was most important. It was also found that the presence of active chlorine led to fewer degradation intermediates compared to treatment in an inert electrolyte.

Evaluation of direct membrane filtration and direct forward osmosis as concepts for compact and energy-positive municipal wastewater treatment

ABSTRACT Municipal wastewater treatment commonly involves mechanical, biological and chemical treatment steps to protect humans and the environment from adverse effects. Membrane technology has gained increasing attention as an alternative to conventional wastewater treatment due to increased urbanization. Among the available membrane technologies, microfiltration (MF) and forward osmosis (FO) have been selected for this study due to their specific characteristics, such as compactness and efficient removal of particles. In this study, two treatment concepts were evaluated with regard to their specific electricity, energy and area demands. Both concepts would fulfil the Swedish discharge demands for small- and medium-sized wastewater treatment plants at full scale: (1) direct MF and (2) direct FO with seawater as the draw solution. The framework of this study is based on a combination of data obtained from bench- and pilot-scale experiments applying direct MF and FO, respectively. Additionally, available complementary data from a Swedish full-scale wastewater treatment plant and the literature were used to evaluate the concepts in depth. The results of this study indicate that both concepts are net positive with respect to electricity and energy, as more biogas can be produced compared to that using conventional wastewater treatment. Furthermore, the specific area demand is significantly reduced. This study demonstrates that municipal wastewater could be treated in a more energy- and area-efficient manner with techniques that are already commercially available and with future membrane technology.

Triazine-based H2S Scavenging: Development of a Conceptual Model for the Understanding of Fouling Formation

The authors studied the applicability of a previously suggested model to describe the reaction between 1,3,5-tri-(2-hydroxypropyl)-hexahydro-s-triazine and H2S and thereby predict formation of fouling. To investigate the reaction system, electrospray ionization mass spectrometry was employed to analyze the composition of the generated mixture as H2S is bubbled through the scavenger. The results of the study confirm that the suggested model is capable of explaining how the scavenger reacts with H2S, which may be used to explain from where and how the fouling originates, and how a scavenging process can be designed to avoid fouling.

Fouling Formation During Hydrogen Sulfide Scavenging With 1,3,5-tri-(hydroxyethyl)-hexahydro-s-triazine

To investigate if the hydrogen sulfide scavenger, 1,3,5-tri-(hydroxyethyl)-hexahydro-s-triazine, could explain a severe carbon/sulfur rich fouling found at a refinery, experiments were conducted to study the scavenging process and the composition of the fouling. The reaction was analyzed with electro spray ionization mass spectrometry (ESI-MS), and the fouling with infrared spectroscopy and X-ray diffraction. The fouling was found to be a by-product of the scavenging reaction, and to consist of dithiazine molecules with linking carbon-sulfur chains. ESI-MS analysis strongly indicates that these chains are generated when dithiazine decomposes to smaller molecules, which through condensation reactions with dithiazine forms the fouling.

Addition of Adsorbents to Nanofiltration Membrane to Obtain Complete Pesticide Removal

Removal of micropollutants from water with NF/RO membranes has received much attention in recent years. However, because of especially diffusion through the polyamide layer, NF/RO membranes never achieve complete removal, which may be a problem given the possibility of micropollutants causing adverse effects in even very low concentrations. In this paper, we have investigated a strategy of implementing adsorbents into the support layer of a NF membrane to increase the overall removal of three selected pesticides by combining membrane rejection and adsorption into one unit operation. The objective of the study was to act as proof of concept for the scheme, as well as to gain insights into how adsorbents may be inserted into the membrane support, and how they affect the membrane performance. The results showed that the addition of the adsorbents to the membrane increased the adsorption capacity of the membrane, and that the adsorbents could be embedded in the membrane without affecting the flux and rejection behaviour. This however depended very much on the specific manufacturing method. Furthermore, the adsorption capacity was found to vary significantly for the three pesticides, indicating a need for adsorbents designed to specifically target a given micropollutant. Overall, the concept of a complete removal membrane is realisable, but several challenges remain to be solved.

Use of ESI-MS to Determine Reaction Pathway for Hydrogen Sulphide Scavenging with 1,3,5-Tri-(2-Hydroxyethyl)-Hexahydro-s-Triazine:

To study the reaction between hydrogen sulphide and 1,3,5-tri-(2-hydroxyethyl)-hexahydro-s-triazine, which is an often used hydrogen sulphide scavenger, electrospray ionisation mass spectrometry (ESI-MS) was used. The investigation was carried out in positive mode and tandem mass spectrometry was used to investigate the nature of unknown peaks in the mass spectra. The reaction was found to proceed as expected from theory with the triazine reacting with hydrogen sulphide to form the corresponding thiadiazine. This species subsequently reacted with a second hydrogen sulphide molecule to form the dithiazine species, thereby confirming previously obtained results and showing the ability of the ESI-MS method for studying the scavenging reaction. The final theoretical product s-trithiane was not detected. Furthermore, fragmentation products of thiadiazine and dithiazine were detected in the solution and possible pathways and structures were suggested to describe the observed fragments. In these, thiadiazine fragmented to 2-(methylidene amino)-ethanol and 2-(1,3-thiazetidin-3-yl)-ethanol and N-(2-hydroxyethyl)-N-(sulfanylmethyl)-ethaniminium, which underwent a further fragmentation to N-methyl-N-(2-oxoethyl)-methaniminium. Dithiazine fragmented to N-methyl-N-(2-oxoethyl)-methaniminium as well. The byproduct from this reaction is methanedithiol, which was not detected due to its low polarity.

Groundwater Chemistry and Treatment: Application to Danish Waterworks

Groundwater is formed by rain infiltrating the soil and subsurface, and as a result, the final composition of the water depends on both the specific geological formations and the residence time of the water in these. With respect to groundwater, the subsurface may be divided into two zones: the unsaturated zone and the saturated zone. In the unsaturated zone, the voids between particles are a mixture of water and air, while in the saturated zone all the voids have been filled with water. The transition from the unsaturated to the saturated zone marks the beginning of the water bearing layers; the groundwater. This is also called the water table.

Separation of Peptides with Forward Osmosis Biomimetic Membranes

Forward osmosis (FO) membranes have gained interest in several disciplines for the rejection and concentration of various molecules. One application area for FO membranes that is becoming increasingly popular is the use of the membranes to concentrate or dilute high value compound solutions such as pharmaceuticals. It is crucial in such settings to control the transport over the membrane to avoid losses of valuable compounds, but little is known about the rejection and transport mechanisms of larger biomolecules with often flexible conformations. In this study, transport of two chemically similar peptides with molecular weight (Mw) of 375 and 692 Da across a thin film composite Aquaporin Inside™ Membrane (AIM) FO membrane was investigated. Despite the relative large size, both peptides were able to permeate the dense active layer of the AIM membrane and the transport mechanism was determined to be diffusion-based. Interestingly, the membrane permeability increased 3.65 times for the 692 Da peptide (1.39 × 10−12 m2·s−1) compared to the 375 Da peptide (0.38 × 10−12 m2·s−1). This increase thus occurs for an 85% increase in Mw but only for a 34% increase in peptide radius of gyration (Rg) as determined from molecular dynamics (MD) simulations. This suggests that Rg is a strong influencing factor for membrane permeability. Thus, an increased Rg reflects the larger peptide chains ability to sample a larger conformational space when interacting with the nanostructured active layer increasing the likelihood for permeation.