Effect of electrolyte composition on electrochemical oxidation: Active sulfate formation, benzotriazole degradation, and chlorinated by-products distribution.

Electrochemical oxidation is an effective technique for treating persistent organic pollutants, which are hardly removed in conventional wastewater treatment plants. Sulfate and chloride salts commonly used and present in natural wastewater influence the electrochemical degradation process. In this study, the effect of electrolyte composition on the active sulfate species (SO4●⁻ and S2O82⁻) formation, benzotriazole degradation-a model organic compound, and chlorinated by-products distribution have been investigated while using a boron-doped diamond (BDD) anode. Different Na2SO4:NaNO3 and Na2SO4:NaCl ratios with constant conductivity of 10 mS/cm were used in the experiments and applied anode potential was kept constant at 4.3 V vs. Ag/AgCl. The electrogenerated SO4●⁻ and S2O82⁻ formation were faster in 10:1 and 2:1 Na2SO4:NaNO3 ratios than in the 1:0 ratio. The ●OH-mediated SO4●⁻ production has prevailed in 10:1 and 2:1 ratios. However, ●OH-mediated SO4●⁻ production has hindered the 1:0 ratio due to excess chemisorption of SO42⁻ on the BDD anode. Similarly, the faster benzotriazole degradation, mineralization, and lowest energy consumption were achieved in the 10:1 Na2SO4:NaNO3 and Na2SO4:NaCl ratio. Besides, chlorinated organic by-product concentration (AOX) was lower in the 10:1 Na2SO4:NaCl ratio but increased with the increasing chloride ratio in the electrolyte. LC-MS analysis shows that several chlorinated organic transformation products were produced in 0:1 to 2:1 ratio, which was not found in the 10:1 Na2SO4:NaCl ratio. A comparatively higher amount of ClO4⁻ was formed in the 10:1 ratio than in 2:1 to 0:1 ratio. This ClO4⁻ formation train evidence the effective ●OH generation in a sulfate-enriched condition because the ClO4⁻ formation is positively correlated to ●OH concentration. Overall results show that sulfate-enriched electrolyte compositions are beneficial for electrochemical oxidation of biorecalcitrant organic pollutants.

Sorption of micropollutants on selected constructed wetland support matrices.

Micropollutants (MPs) are organic chemicals that are present in the environment at low concentrations (ng/L-µg/L), for example pharmaceuticals. A constructed wetland (CW) is a promising post-treatment technique to remove MPs from wastewater effluent. Selecting a suitable material for support matrix is important when designing such a CW. Nine materials were studied as potential support matrices: Light Expanded Clay Aggregates (LECA), compost, bark, granulated activated carbon (GAC), biochar, granulated cork, lava rock, sand and gravel. Batch experiments were conducted to study MP removal by nine materials in phosphate buffer with 5 or 50 µg/L MPs, or wastewater effluent with 50 µg/L of MPs. GAC and biochar removed almost all MPs in both phosphate buffer and wastewater effluent, followed by bark, compost, granulated cork. Sand, gravel, LECA and lava rock removed less than 30% of most MPs in both matrixes. Based on set criteria (e.g. removal efficiency), biochar, bark, compost, LECA and sand were selected, and used in combinations in column studies to test their overall performance. A combination of bark and biochar performed the best on MP removal, as 4 MPs were highly (70%-100%) removed, 4 MPs were moderately (30%-70%) removed while only 3 MPs were hardly removed. The main flow regime of this combination was both plug flow and dispersive flow. Moreover, we hypothesized to apply bark and biochar in a CW. Based on the assumptions and calculations, some benefits are expected, such as increasing MP removal and extending operation time.

Bioflocculants from wastewater: Insights into adsorption affinity, flocculation mechanisms and mixed particle flocculation based on biopolymer size-fractionation.

HYPOTHESIS: Microbial extracellular polymeric substances (EPS) produced from wastewater are generally heterodispersed, which is expected to influence their flocculation performances and mechanism, particularly in mixed particle systems. The different molecular weight (MW) fractions should contribute to the overall adsorption affinity and flocculation mechanism of EPS in single and dual clay systems. EXPERIMENTS: EPS harvested from bioreactors were size-fractionated into high, medium and low MW fractions (HMW, MMW, LMW, respectively). The harvested mixed EPS and its fractions were characterised by diverse analytical techniques coupled with optical reflectometry to investigate the role of each EPS fraction in the overall flocculation mechanism of EPS in kaolinite and montmorillonite clay systems. FINDINGS: In single clay systems, both the harvested mixed EPS and the HMW-EPS fraction showed comparable flocculation performances. However, mixed EPS proved to be more efficient than the HMW-EPS fraction for dual clay flocculation. Site blocking effects were observed in mixed EPS: the LMW and MMW EPS first adsorbed to the surface due to higher diffusivities and faster mass transfer to the interface, while the HMW-EPS were slowly transported but were attached to the surface irreversibly and stronger than the LMW/MMW-EPS. We propose from this, a mixed EPS adsorption mechanism: extended anionic polymer tails in solution, thereby enhancing particle flocculation.

Experimental Evaluation of Anion Exchange Membranes for the Desalination of (Waste) Water Produced after Polymer-Flooding.

Electrodialysis (ED) has been recently proposed to desalinate polymer-flooding produced water (PFPW), a byproduct stream from the oil and gas industry rich in charged polymers. However, process performance is limited by fouling occurring on the ion-exchange membranes, particularly on the anionic ones (AEMs). Thus, this study aimed to correlate the properties of different AEMs with their performance while desalinating PFPW, ultimately evaluating their significance when fouling is to be minimized and operation improved. Six stacks containing different homogeneous and commercially available AEMs were employed to desalinate synthetic PFPW during 8-days ED experiments operated in reversal mode. AEMs recovered from the stacks were analyzed in terms of water uptake, ion-exchange capacity, permselectivity, and area resistance, and compared with virgin AEMs. Relatively small changes were measured for most of the parameters evaluated. For most AEMs, the water uptake and resistance increased, while the ion-exchange capacity (IEC) and permselectivity decreased during operation. Ultimately, AEMs with high area resistance were linked to the fast development of limiting current conditions in the stack, so this property turned out to be the most relevant when desalinating PFPW.

Removal of organic compounds from cooling tower blowdown by electrochemical oxidation: Role of electrodes and operational parameters.

The reuse of cooling tower blowdown (CTBD) in the cooling tower itself requires CTBD deionization and a pre-treatment before deionization to remove organic compounds (OCs) that induce membrane fouling. This study assesses the potential of electrochemical oxidation (EO) with a boron-doped diamond (BDD) and a Ti/RuO2 mixed-metal oxide (MMO) anode for CTBD pre-treatment. Also, the influence of the applied current density (j), initial pH, hydrodynamic conditions, and supporting electrolyte on the process performance was evaluated. Results show that COD and TOC removal were 85 and 51%, respectively, with the BDD-anode; however, they were 50 and 12% with MMO-anode at a j-value of 8.7 mA cm-2 and neutral pH. An increased j-value increased the COD and TOC removal; however, different pHs, hydrodynamic conditions, and the addition of supporting electrolytes had a minor impact on the removal with both anodes. Liquid chromatography-organic carbon detection analysis showed that the OC in CTBD mainly consisted of humic substances (HS). EO with the BDD-anode resulted in 35% HS mineralization, while the rest of the HS were partially oxidized into low molecular weight compounds and building blocks. However, HS mineralization was limited with the MMO-anode. The mineralization and oxidation were accompanied by the formation of organic and inorganic chlorinated species. These species increased the toxicity to Vibrio fischeri 20-fold compared to the initially low-toxic CTBD. Thus, EO with a BDD-anode is a promising pre-treatment technology for the removal of OCs before CTBD deionization, but measures to minimize the chlorinated species formation are required before its application.

Regeneration and reuse of microbial extracellular polymers immobilised on a bed column for heavy metal recovery.

Microbial extracellular polymeric substances (EPS) have gained increasing attention for various water treatment applications. In this study, EPS produced from nitrogen-limited glycerol/ethanol-rich wastewater were used to recover Cu2+ and Pb2+ from aqueous solutions. Continuous flow-through tests were conducted on a column packed with silica gel coated with polyethyleneimine, to which EPS were irreversibly attached as shown by optical reflectometry. These immobilised EPS excellently adsorbed Cu2+ and Pb2+, with 99.9% of influent metal adsorbed before the breakthrough points. Metal desorption was achieved with 0.1M HCl, with an average recovery of 86% for Cu2+ and 90% recovery for Pb2+. For the first time, we successfully showed the possibility to regenerate and reuse the immobilised EPS for five adsorption-desorption cycles (using Cu2+ as an example) with no reduction in the adsorbed amount at the breakthrough point (qbp). Based on the mass balance of the associated metal ions participating in the adsorption process, ion exchange was identified as the major mechanism responsible for Cu2+ and Pb2+ adsorption by EPS. The results demonstrate the potential of wastewater-produced EPS as an attractive and perhaps, cost-effective biosorbent for heavy metal removal (to trace effluent concentrations) and recovery (86-99%).

Valorization of glycerol/ethanol-rich wastewater to bioflocculants: recovery, properties, and performance.

Microbial extracellular polymeric substances (EPS) were produced in two membrane bioreactors, each separately treating fresh and saline synthetic wastewater (consisting of glycerol and ethanol), with the purpose of applying them as sustainable bioflocculants. The reactors were operated under nitrogen-rich (COD/N ratios of 5 and 20) and limited (COD/N ratios of 60 and 100) conditions. Under both conditions, high COD removal efficiencies of 87-96% were achieved. However, nitrogen limitation enhanced EPS production, particularly the polysaccharide fraction. The maximum EPS recovery (g EPS-COD/g CODinfluent) from the fresh wastewater was 54% and 36% recovery was obtained from the saline (30 g NaCl/L) wastewater. The biopolymers had molecular weights up to 2.1 MDa and anionic charge densities of 2.3-4.7 meq/g at pH 7. Using kaolin clay suspensions, high flocculation efficiencies of 85-92% turbidity removal were achieved at EPS dosages below 0.5 mg/g clay. Interestingly, EPS produced under saline conditions proved to be better flocculants in a saline environment than the corresponding freshwater EPS in the same environment. The results demonstrate the potential of glycerol/ethanol-rich wastewater, namely biodiesel/ethanol industrial wastewater, as suitable substrates to produce EPS as effective bioflocculants.

Estimation of the water cycle related to shale gas production under high data uncertainties: Dutch perspective.

The potential water demand for fracturing fluids along with the possible flowback and produced water production is assessed for the Dutch Posidonia shale. Total water demand estimated for 25 years of the field development using historic data from the U.S. plays varies between 12.2 and 36.9 Mm3. The maximal annual water consumption of 0.95-2.88 Mm3 is expected in the peak years of shale gas production. These figures are much lower than the availability of any potential water sources, which include drinking water, fresh and brackish groundwater, river water, effluents of wastewater treatment plants (WWTP) and sea water. River water is considered the most promising water source for fracturing fluids in the Dutch Posidonia shale based on its availability (>6·104 Mm3/year) and quality (only bacterial composition needs to be controlled). Total wastewater production for the whole period of the field development is estimated between 6.6 and 48.0 Mm3. Wastewater recycling can cover significant part of the source water demand for fracturing fluid. However, high mineral content of the wastewater as well as temporal and spatial discrepancies between wastewater production and water demand will form obstacles for wastewater recycling. The assessment framework developed in this study may be applied for other shale gas fields with high uncertainties regarding subsurface properties, connate formation water characteristics and future legislative framework.

Removal of organic compounds from shale gas flowback water.

Ozonation, sorption to granular activated carbon and aerobic degradation were compared as potential treatment methods for removal of dissolved organic carbon (DOC) fractions and selected organic compounds from shale gas flowback water after pre-treatment in dissolved air flotation unit. Flowback water was characterised by high chemical oxygen demand and DOC. Low molecular weight (LMW) acids and neutral compounds were the most abundant organic fractions, corresponding to 47% and 35% of DOC respectively. Ozonation did not change distribution of organic carbon fractions and concentrations of detected individual organic compounds significantly. Sorption to activated carbon targeted removal of individual organic compounds with molecular weight >115 Da, whereas LMW compounds remained largely unaffected. Aerobic degradation was responsible for removal of LMW compounds and partial ammonium removal, whereas formation of intermediates with molecular weight of 200-350 Da was observed. Combination of aerobic degradation for LMW organics removal with adsorption to activated carbon for removal of non-biodegradable organics is proposed to be implemented between pre-treatment (dissolved air floatation) and desalination (thermal or membrane desalination) steps.

Nitrogen removal performance and microbial community changes in subsurface wastewater infiltration systems (SWISs) at low temperature with different bioaugmentation strategies.

Poor nitrogen removal efficiency (mainly nitrate, NO3--N) at low temperatures strongly limits application of subsurface wastewater infiltration systems (SWISs). Seven psychrophilic strains (heterotrophic nitrifying bacteria and aerobic denitrifying bacteria) were isolated and added to SWISs to investigate the effect of embedding and direct-dosing bioaugmentation strategies on sewage treatment performance at low temperature. Both bioaugmentation strategies improved ammonium (NH4+-N) removal efficiencies, and the embedding strategy also exhibited satisfactory NO3--N and total nitrogen (TN) removal efficiencies. Pyrosequencing results of the bacterial 16S rRNA gene indicated that the embedding strategy significantly decreased the indigenous soil microbial diversity (p < .05) and altered the bacterial community structure, significantly increasing the relative abundance of Clostridia, which have good nitrate-reducing activity.

Organic Pollutants in Shale Gas Flowback and Produced Waters: Identification, Potential Ecological Impact, and Implications for Treatment Strategies.

Organic contaminants in shale gas flowback and produced water (FPW) are traditionally expressed as total organic carbon (TOC) or chemical oxygen demand (COD), though these parameters do not provide information on the toxicity and environmental fate of individual components. This review addresses identification of individual organic contaminants in FPW, and stresses the gaps in the knowledge on FPW composition that exist so far. Furthermore, the risk quotient approach was applied to predict the toxicity of the quantified organic compounds for fresh water organisms in recipient surface waters. This resulted in an identification of a number of FPW related organic compounds that are potentially harmful namely those compounds originating from shale formations (e.g., polycyclic aromatic hydrocarbons, phthalates), fracturing fluids (e.g., quaternary ammonium biocides, 2-butoxyethanol) and downhole transformations of organic compounds (e.g., carbon disulfide, halogenated organic compounds). Removal of these compounds by FPW treatment processes is reviewed and potential and efficient abatement strategies are defined.

UASB reactor effluent disinfection by ozone and chlorine.

This research studied the sequential ozone and chlorine process with respect to, the inactivation of indicator bacteria and the formation of ozone disinfection byproducts in sanitary wastewater effluent. The applied ozone doses were 5, 8 and 10 mg.O3.L(-1), followed by chlorine doses of 10, 20 and 30 mg.L(-1), respectively. After the sequential ozone/chlorine process, the mean reduction in chemical oxygen demand ranged from 9 to 37%. Total coliform inactivation ranged from 1.59 to 3.73 log10, and E. coli was always <1 CFU 100 mL(-1). Ozonation resulted in the formation of aldehydes, which were not significantly impacted by the subsequent chlorine dose (P ≤ 0.05).

Effect of granular activated carbon concentration on the content of organic matter and salt, influencing E. coli activity and survival in fluidized bed disinfection reactor.

Granular activated carbon (GAC) is used in water treatment systems, typically to remove pollutants such as natural organic matter, volatile organic compounds, chlorine, taste, and odor. GAC is also used as a key component of a new technology that combines a fluidized bed reactor with radio frequency electric fields for disinfection. So far, the effects of GAC on bacteria in these fluidized bed reactors are unclear. This paper describes a systematic study of the physico-chemical changes in five microbial media compositions caused by different concentrations (23-350 g/L) of GAC, and the effects of these physico-chemical changes on the metabolic activity and survival of a model microorganism (Escherichia coli YMc10) in a fluidized bed reactor. The chemical adsorption taking place in suspensions with specific GAC changed nutritional, osmotic, and pH conditions in the investigated microbial media (LB, diluted LB, PBS, diluted PBS, and tap water), leading to a decay of the metabolic activity and survival of E. coli. Especially media that are poor in organic and mineral compounds (e.g., PBS) with suspended GAC showed a concentration decay of 3.5 Log CFU/mL E. coli after 6 h. Organic compounds depletion and severe pH variation were enhanced in the presence of higher GAC concentrations.

Alternating electric fields combined with activated carbon for disinfection of Gram negative and Gram positive bacteria in fluidized bed electrode system.

Strong electric fields for disinfection of wastewaters have been employed already for several decades. An innovative approach combining low strength (7 V/cm) alternating electric fields with a granular activated carbon fluidized bed electrode (FBE) for disinfection was presented recently. For disinfection performance of FBE several pure microbial cultures were tested: Bacillus subtilis, Bacillus subtilis subsp. subtilis, Enterococcus faecalis as representatives from Gram positive bacteria and Erwinia carotovora, Pseudomonas luteola, Pseudomonas fluorescens and Escherichia coli YMc10 as representatives from Gram negative bacteria. The alternating electric field amplitude and shape were kept constant. Only the effect of alternating electric field frequency on disinfection performance was investigated. From the bacteria tested, the Gram negative strains were more susceptible and the Gram positive microorganisms were more resistant to FBE disinfection. The collected data indicate that the efficiency of disinfection is frequency and strain dependent. During 6 h of disinfection, the decrease above 2 Log units was achieved with P. luteola and E. coli at 10 kHz and at dual frequency shift keying (FSK) modulated signal with frequencies of 10 kHz and 140 kHz. FBE technology appears to offer a new way for selective bacterial disinfection, however further optimizations are needed on treatment duration, and energy input, to improve effectiveness.

Biochemical ripening of dredged sediments. Part 1. Kinetics of biological organic matter mineralization and chemical sulfur oxidation.

After dredged sediments have settled in a temporary upland disposal site, ripening starts, which turns waterlogged sediment into aerated soil. Aerobic biological mineralization of organic matter (OM) and chemical oxidation of reduced sulfur compounds are the major biochemical ripening processes. Quantitative data describing these processes are scarce. Therefore, aerobic oxidation and mineralization of five previously anaerobic dredged sediments were studied during a 160-d laboratory incubation experiment at 30 degrees C. A double exponential decay model could adequately describe sulfur oxidation and OM mineralization kinetics. During the first 7 d of incubation, 23 to 80% of the total sulfur was oxidized, after which no further sulfur oxidation was observed. Oxygen used for sulfur oxidation amounted up to 95% of the total oxygen uptake in the first 7 d and up to 45% of the oxygen uptake during the entire incubation period. Mineralization rates of the rapidly mineralizable OM fractions that degraded during the first 14 to 28 d of incubation were 10(2) to 10(3) times higher than the mineralization rates of the slowly mineralizable OM during the remaining period. First-order mineralization rates of the slowly mineralizable OM were 0.22 x 10(-3) to 0.54 x 10(-3) d(-1) and can be compared with those of terrestrial soils. Yields of biomass on substrate ranged from 0.08 to 0.45 g C(biomass)/g C(OM) and appeared to be higher for rapidly mineralizing OM than for slowly mineralizing OM. The results of this study can be used to optimize conditions during temporary disposal of sediments, to estimate the potential decrease in OM, and for future studies on the possible link between OM mineralization and degradation of hydrophobic organic contaminants.

Biochemical ripening of dredged sediments. Part 2. Degradation of polycyclic aromatic hydrocarbons and total petroleum hydrocarbons in slurried and consolidated sediments.

Ripening of polycyclic aromatic hydrocarbons (PAH) and total petroleum hydrocarbons (TPH) polluted dredged sediment can be considered as a bioremediation technique. Aerobic biodegradation of PAH and TPH was studied in five previously anaerobic-slurried sediments during a 350-d laboratory incubation experiment. In addition, oxygen penetration and degradation of PAH and TPH were studied in three consolidated (physically ripened) sediments. All experiments were conducted in the laboratory at 30 degrees C. A double exponential decay model could adequately describe PAH and TPH degradation kinetics in the slurried sediments. First-order degradation rate constants for the rapidly degradable fractions (12-58%) were approximately 0.13 and 0.058 d(-1) for PAH and TPH, respectively, whereas the rate constants for the slowly degradable fractions were approximately 0.36 x 10(-3) (PAH) and 0.66 x 10(-3) d(-1) (TPH). Rate constants for the rapidly and slowly degrading fractions have the same order of magnitude as the mineralization rate constants of the rapidly and slowly mineralizing organic matter (OM) fractions in the sediments. Oxygen uptake by degradation of PAH and TPH was negligible compared to the oxygen uptake by sulfur oxidation and OM mineralization. In consolidated sediments, PAH and TPH degradation was limited to the oxygenated part. Amounts of PAH and TPH that degraded in the oxygenated parts of the consolidated sediments during 21 d of incubation were similar to the amounts that degraded during 21 d in the slurried sediments.