Sulfide-iron interactions in domestic wastewater from a gravity sewer

Interactions between iron and sulfide in domestic wastewater from a gravity sewer were investigated with particular emphasis on redox cycling of iron and iron sulfide formation. The concentration ranges of iron and total sulfide in the experiments were 0.4-5.4mgFeL(-1) and 0-5.1mgSL(-1), respectively. During anaerobic conditions, iron reduction kinetics were investigated and reduction rates amounted on average to 1.32mgFeL(-1)d(-1). Despite the very low solubility of iron sulfide, the reduced iron reacted only partly with sulfide to produce iron sulfide, even when dissolved sulfide was in excess. When a ferric chloride solution was added to sulfide containing anaerobic wastewater, the ferric iron was quickly reduced to ferrous forms by oxidation of dissolved sulfide and the ferrous iron precipitated almost completely as iron sulfide. During aerobic conditions, iron sulfide was oxidized with a half-life period of 11.7h. The oxidation rate of iron sulfide was significantly lower than that reported for the oxidation of dissolved sulfide.     

Iron crystallization in a fluidized-bed Fenton process

The mechanisms of iron precipitation and crystallization in a fluidized-bed reactor were investigated. Within the typical Fenton’s reagent dosage and pH range, ferric ions as a product from ferrous ion oxidation would be supersaturated and would subsequently precipitate out in the form of ferric hydroxide after the initiation of the Fenton reaction. These precipitates would simultaneously crystallize onto solid particles in a fluidized-bed Fenton reactor if the precipitation proceeded toward heterogeneous nucleation. The heterogeneous crystallization rate was controlled by the fluidized material type and the aging/ripening period of the crystallites. Iron crystallization onto the construction sand was faster than onto SiO₂, although the iron removal efficiencies at 180 min, which was principally controlled by iron hydroxide solubility, were comparable. To achieve a high iron removal rate, fluidized materials have to be present at the beginning of the Fenton reaction. Organic intermediates that can form ferro-complexes, particularly volatile fatty acids, can significantly increase ferric ion solubility, hence reducing the crystallization performance. Therefore, the fluidized-bed Fenton process will achieve exceptional performance with respect to both organic pollutant removal and iron removal if it is operated with the goal of complete mineralization. Crystallized iron on the fluidized media could slightly retard the successive crystallization rate; thus, it is necessary to continuously replace a portion of the iron-coated bed with fresh media to maintain iron removal performance. The iron-coated construction sand also had a catalytic property, though was less than those of commercial goethite.     

Pharmaceutical wastewater degradation: effective and economical treatment using waste-metallic iron shavings

Industrial wastewater generated by a drug manufacturing plant located in Spain was degraded by Fenton oxidation processes, which employ waste-metallic iron shavings as heterogeneous zero-valent iron (ZVI) catalyst and hydrogen peroxide. The effluent comprises a complex mixture of organic substances which are very refractory to common conventional treatments and it is characterized by a low BOD/COD ratio. The stirring speed or the particle size has been found to be the determining factors, greatly influencing the degradation of the organic pollutants present in the wastewater. The influence of the initial hydrogen peroxide concentration has also been evaluated. The optimal conditions for degradation led to total organic carbon (TOC) reductions of up to 60%. The remarkable results of TOC mineralization could also be attributed to the physico-chemical modification of the ZVI during the oxidizing process. This study shows that the ZVI/H₂O₂ system can be considered as an easy, economic and effective alternative solution as a pre-treatment step before biological treatments.     

Assessing wastewater metal toxicity with bacterial bioluminescence in a bench-scale wastewater treatment system

The effectiveness of a previously developed toxicity monitoring method for activated sludge wastewater treatment employing a bioluminescent bacterium (Shk1) was evaluated in batch experiments and a bench-scale activated sludge system exposed to heavy metals (Cu, Zn, Ni, and Cd). Influent wastewater (primary clarifier supernatant) and activated sludge from a municipal wastewater treatment plant were used in both batch experiments and in the bench-scale wastewater treatment system. Shk1 bioluminescence was most sensitive to Cd and Zn, followed by Cu, and then Ni in order of decreasing sensitivity. In contrast, activated sludge specific oxygen uptake rate was most sensitive to Cu, followed by Cd and Zn, and finally Ni. The same pattern of sensitivity was observed in batch and bench-scale evaluations. Batch experiments examining the effect of metal adsorption were performed. The adsorption of metals to activated sludge and reduction in bioavailability due to chelation by soluble organics or by precipitation in wastewater was found to be an important effect in mediating differences in toxicity response between bioluminescence and respirometry. Batch adsorption experiments indicated that the activated sludge adsorption capacity was highest for Cu, followed by Cd, Ni, and then Zn. A simple mathematical model for the soluble metal concentration in the aeration basin and clarifier was developed utilizing metal distribution coefficients determined from the batch adsorption experiments. Model predictions compared well with results from the bench-scale activated sludge experiments.     

Minimization of excess sludge production for biological wastewater treatment

Excess sludge treatment and disposal currently represents a rising challenge for wastewater treatment plants (WWTPs) due to economic, environmental and regulation factors. There is therefore considerable impetus to explore and develop strategies and technologies for reducing excess sludge production in biological wastewater treatment processes. This paper reviews current strategies for reducing sludge production based on these mechanisms: lysis-cryptic growth, uncoupling metabolism, maintenance metabolism, and predation on bacteria. The strategies for sludge reduction should be evaluated and chosen for practical application using costs analysis and assessment of environmental impact. High costs still limit technologies of sludge ozonation-cryptic growth and membrane bioreactor from spreading application in full-scale WWTPs. Bioacclimation and harmful to environment are major bottlenecks for chemical uncoupler in practical application. Sludge reduction induced by oligochaetes may present a cost-effective way for WWTPs if unstable worm growth is solved. Employing any strategy for reducing sludge production may have an impact on microbial community in biological wastewater treatment processes. This impact may influence the sludge characteristics and the quality of effluent.     

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 2600 Da was the main colloidal component. High molar mass fractions (HMM), with molar mass ranges between 20 and 200 kDa, were present in lower proportions. Ag, Cd, Cu, Cr, Mn and Zn were found mainly in the dissolved phase (<0.45 μm) 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.     

Control of the sulfide (S2-) concentration for optimal zinc removal by sulfide precipitation in a continuously stirred tank reactor

Precipitation of Zn2+ with S2- was studied at room temperature in a continuously stirred tank reactor of 0.5l to which solutions of ZnSO4 (800-5800 mgl(-1) Zn2+) and Na2S were supplied. The pH was controlled at 6.5 and S2- concentration in the reactor was controlled at set point values ranging from 3.2x10(-19) to 3.2x10(-4) mgl(-1), making use of an ion-selective S2- electrode. In steady state, the mean particle size of the ZnS precipitate decreased linearly from 22 to 1 microm for S2- levels dropping from 3.2x10(-4) to 3.2x10(-18) mgl(-1). At 3.2x10(-11) mgl(-1) of S2-, the supplies of ZnSO4 and Na2S solutions were stoichiometric for ZnS precipitation. At this S2- level, removal of dissolved zinc was optimal with effluent zinc concentration <0.03 mgl(-1) while ZnS particles formed with a mean geometric diameter of about 10 microm. Below 3.2x10(-11) mgl(-1) of S2- insufficient sulfide was added for complete zinc precipitation. At S2- levels higher than 3.2x10(-11) mgl(-1) the effluent zinc concentration increased due to the formation of soluble zinc sulfide complexes as confirmed by chemical equilibrium model calculations.     

Toxicity of fluoride to microorganisms in biological wastewater treatment systems

Fluoride is a common contaminant in a variety of industrial wastewaters. Available information on the potential toxicity of fluoride to microorganisms implicated in biological wastewater treatment is very limited. The objective of this study was to evaluate the inhibitory effect of fluoride towards the main microbial populations responsible for the removal of organic constituents and nutrients in wastewater treatment processes. The results of short-term batch bioassays indicated that the toxicity of sodium fluoride varied widely depending on the microbial population. Anaerobic microorganisms involved in various metabolic steps of anaerobic digestion processes were found to be very sensitive to the presence of fluoride. The concentrations of fluoride causing 50% metabolic inhibition (IC₅₀) of propionate- and butyrate-degrading microorganisms as well as mesophilic and thermophilic acetate-utilizing methanogens ranged from 18 to 43 mg/L. Fluoride was also inhibitory to nitrification, albeit at relatively high levels (IC₅₀ = 149 mg/L). Nitrifying bacteria appeared to adapt rapidly to fluoride, and a near complete recovery of their metabolic activity was observed after only 4 d of exposure to high fluoride levels (up to 500 mg/L). All other microbial populations evaluated in this study, i.e., glucose fermenters, aerobic glucose-degrading heterotrophs, denitrifying bacteria, and H₂-utilizing methanogens, tolerated fluoride at very high concentrations (>500 mg/L).     

Phosphatase activity in anaerobic bioreactors for wastewater treatment

Phosphatase (PO4ase) activity was investigated in continuous and fed-batch anaerobic bioreactors for wastewater treatment. PO4ase levels were high in continuously fed reactors (880-2632 micromol/L/h), compared to a fed-batch reactor (FBR) (540-1249 micromol/L/h). Alkaline and acid PO4ases were present in all the reactors, but in varying magnitudes and total PO4ase activity exhibited a 10-30% variation even at steady-state reactor conditions. The PO4ase activity was not affected by the inorganic phosphate (Pi) level in the reactors, but biomass level and wastewater type, including specific PO4ases (either alkaline or acid), strongly influenced the PO4ase activity in a reactor. Both flocculated and suspended cells produced PO4ase, and 60-65% of the enzyme was cell bound, remaining entrapped in the extracellular matrix and in cell-free form. Batch studies with anaerobic sludge showed a negative correlation between Pi and PO4ase activity. An increase in PO4ase activity was observed under starvation and higher salinity (above 15 g/L). Glucose and propionate (at 10 mM level) induced PO4ase activity, whereas acetate and butyrate (10 mM) addition had no response. This study also reveals that Archaea and bacteria contributed 45% and 55%, respectively, of total PO4ase activity in anaerobic sludge.     

Persistence and prevalence of pathogenic and extended-spectrum beta-lactamase-producing Escherichia coli in municipal wastewater treatment plant receiving slaughterhouse wastewater

We compared the prevalence of pathogenic and extended-spectrum beta-lactamase (ESBL) – producing Escherichia coli in effluents of a municipal wastewater treatment plant (WWTP) receiving wastewater from a slaughterhouse. A total of 1248 isolates were screened for the presence of virulence genes associated with enterohemorrhagic E. coli (EHEC) (stx₁, stx₂, and eae) and extraintestinal pathogenic E. coli (ExPEC) (sfa/focDE, kpsMT K1, hlyA, papEF, afa/draBC, clbN, f17A and cnf). The prevalence of atypical enteropathogenic E. coli (EPEC) was 0.7%, 0.2% and 0.5% in city wastewater, slaughterhouse wastewater and in the treated effluent, respectively. One stx_1a and stx_2b-positive E. coli isolate was detected in city wastewater. The prevalence of ExPEC was significantly higher in city wastewater (8.4%), compared to slaughterhouse wastewater (1.2%). Treatment in the WWTP did not significantly impact the prevalence of ExPEC in the outlet effluent (5.0%) compared to city wastewater. Moreover, the most potentially pathogenic ExPEC were isolated from city wastewater and from the treated effluent. ESBL-producing E. coli was also mainly detected in city wastewater (1.7%), compared to slaughterhouse wastewater (0.2%), and treated effluent (0.2%). One ESBL-producing E. coli, isolated from city wastewater, was eae-β1 positive. These results showed that pathogenic and/or ESBL-producing E. coli were mainly detected in human wastewater, and at a lesser extend in animal wastewater. Treatment failed to eliminate these strains which were discharged into the river, and then these strains could be transmitted to animals and humans via the environment.     

Occurrence, partition and removal of pharmaceuticals in sewage water and sludge during wastewater treatment

During 8 sampling campaigns carried out over a period of two years, 72 samples, including influent and effluent wastewater, and sludge samples from three conventional wastewater treatment plants (WWTPs), were analyzed to assess the occurrence and fate of 43 pharmaceutical compounds. The selected pharmaceuticals belong to different therapeutic classes, i.e. non-steroidal anti-inflammatory drugs, lipid modifying agents (fibrates and statins), psychiatric drugs (benzodiazepine derivative drugs and antiepileptics), histamine H2-receptor antagonists, antibacterials for systemic use, beta blocking agents, beta-agonists, diuretics, angiotensin converting enzyme (ACE) inhibitors and anti-diabetics. The obtained results showed the presence of 32 target compounds in wastewater influent and 29 in effluent, in concentrations ranging from low ng/L to a few μg/L (e.g. NSAIDs). The analysis of sludge samples showed that 21 pharmaceuticals accumulated in sewage sludge from all three WWTPs in concentrations up to 100 ng/g. This indicates that even good removal rates obtained in aqueous phase (i.e. comparison of influent and effluent wastewater concentrations) do not imply degradation to the same extent. For this reason, the overall removal was estimated as a sum of all the losses of a parent compound produces by different mechanisms of chemical and physical transformation, biodegradation and sorption to solid matter. The target compounds showed very different removal rates and no logical pattern in behaviour even if they belong to the same therapeutic groups. What is clear is that the elimination of most of the substances is incomplete and improvements of the wastewater treatment and subsequent treatments of the produced sludge are required to prevent the introduction of these micro-pollutants in the environment.     

Antimicrobial resistance of fecal indicators in municipal wastewater treatment plant

Antimicrobial resistance of fecal coliforms (n = 153) and enterococci (n = 199) isolates was investigated in municipal wastewater treatment plant (WWTP) based on activated sludge system. The number of fecal indicators (in influent and effluent as well as in the aeration chamber and in return activated sludge mixture) was determined using selective media. Susceptibility of selected strains was tested against 19 (aminoglycosides, aztreonam, carbapenems, cephalosporins, β-lactam/β-lactamase inhibitors, fluoroquinolones, penicillines, tetracycline and trimethoprim/sulfamethoxazole) and 17 (high-level aminoglycosides, ampicillin, chloramphenicol, erythromycin, fluoroquinolones, glycopeptides, linezolid, lincosamides, nitrofuration, streptogramins, tetracycline) antimicrobial agents respectively. Among enterococci the predominant species were Enterococcus faecium (60.8%) and Enterococcus faecalis (22.1%), while remaining isolates belonged to Enterococcus hirae (12.1%), Enterococcus casseliflavus/gallinarum (4.5%), and Enterococcus durans (0.5%). Resistance to nitrofuration and erythromycin was common among enterococci (53% and 44%, respectively), and followed by resistance to ciprofloxacin (29%) and tetracycline (20%). The resistance phenotypes related to glycopeptides (up to 3.2%) and high-level aminoglycosides (up to 5.4%) were also observed. Most frequently, among Escherichia coli isolates the resistance patterns were found for ampicillin (34%), piperacillin (24%) and tetracycline (23%). Extended-spectrum β-lactamase producing E. coli was detected once, in the aeration chamber. In the study the applied wastewater treatment processes considerably reduced the number of fecal indicators. Nevertheless their number in the WWTP effluent was higher than 10⁴ CFU per 100 ml and periodically contained 90% of bacteria with antimicrobial resistance patterns. The positive selection of isolates with antimicrobial resistance patterns was observed during the treatment processes. Substantial concern should be paid to the isolates resistant to 3 or more chemical classes of antimicrobials (MAR). In treated wastewater MAR E. coli and MAR enterococci constituted respectively 9% and 29% of tested isolates.     

Predicting metals partitioning in wastewater treatment plant influents

Interactions of heavy metals with primary sludge particulates were investigated using batch equilibrium metal uptake experiments. Results showed that metal uptake by primary sludge is significantly affected by pH. A mathematical model was developed to describe metals partitioning as a function of pH. The metal adsorption constants were determined. Results showed that for the same metal ion, the values of metal adsorption constants for primary sludge samples collected from different locations and at different times were in the same order of magnitude. Therefore, the adsorption constants were normalized and calibrated using field data. For Ag(I), Cd(II), Co(II), Cr(III), Cu(II), Ni(II), Pb(II), and Zn(II), the calibrated values of adsorption constants (logK(S)) are, respectively, 4.4, 5.1, 3.6, 4.5, 4.6, 3.6, 6.0, and 6.0. These constants can be used to predict the metal partitioning in plant influents and metal removal in primary treatment processes.     

Occurrence and fate of TMDD in wastewater treatment plants in Germany

The occurrence and fate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD) was investigated in four wastewater treatment plants (WWTPs) in Germany. The concentration of TMDD in influents and effluents in the WWTPs ranged from 134 ng/L to 5846 ng/L and from <LOQ to 3539 ng/L correspondingly. Loads determined in influents (10.1 g/d-1142 g/d) and effluents (<LOQ - 425 g/d) indicate that TMDD is partially removed from the wastewater. The elimination rates varied between 33% and 68%. Based on the load analysis, the TMDD effluent discharge of WWTPs investigated varied from 8.29 kg/a to 52.6 kg/a. Day and week profiles were recorded and indicated that TMDD is introduced into the sewage through household and indirect dischargers with high fluctuations. Seasonal variations in the TMDD loads were also analyzed in three of the studied WWTPs. One of the WWTPs demonstrated statistically higher TMDD loads during the warm period (164 g/d) than during the cold period (91.3 g/d), for the others WWTPs any differences could not be established. The input of TMDD during weekends and working days was also studied. The results did not show any significant trend of TMDD discharge into the WWTPs.     

Distribution of antidepressant residues in wastewater and biosolids following different treatment processes by municipal wastewater treatment plants in Canada

The fate of 14 antidepressants along with their respective N-desmethyl metabolites and the anticonvulsive drug carbamazepine (CBZ) was studied in 5 different sewage treatment plants (STPs) across Canada. Using two validated LC-MS/MS analytical methods, the concentrations of the different compounds were determined in raw influent, final effluent and treated biosolids samples. Out of the 15 compounds investigated, 13 were positively detected in most 24-h composite raw influent samples. Analysis showed that venlafaxine (VEN), its metabolite O-desmethylvenlafaxine (DVEN), citalopram (CIT), and CBZ were detected at the highest concentrations in raw influent (up to 4.3 μg L⁻¹ for DVEN). Cumulated results showed strong evidence that primary treatment and trickling filter/solids contact has limited capacity to remove antidepressants from sewage, while activated sludge, biological aerated filter, and biological nutrient removal processes yielded moderate results (mean removal rates: 30%). The more recalcitrant compounds to be eliminated from secondary STPs were VEN, DVEN and CBZ with mean removal rates close to 12%. Parent compounds were removed to a greater degree than their metabolites. The highest mean concentrations in treated biosolids samples were found for CIT (1033 ng g⁻¹), amitriptyline (768 ng g⁻¹), and VEN (833 ng g⁻¹). Experimental sorption coefficients (K_d) were also determined. The lowest K_d values were obtained with VEN, DVEN, and CBZ (67-490 L kg⁻¹). Sorption of these compounds on solids was assumed negligible (log K_d ≤ 2). However, important sorption on solids was observed for sertraline, desmethylsertraline, paroxetine and fluoxetine (log K_d > 4).     

Productivity of wastewater treatment plants in the Valencia Region of Spain

This study analyses the evolution of productivity over the 2008–2012 period for a homogenous set of 199 wastewater treatment plants that are located in the Valencia Region of Spain and utilize the same treatment technology, using the smoothed bootstrap Malmquist productivity index based on Data Envelopment Analysis (DEA). The results reveal a negative trend in productivity that is mainly the result of resource management rather than an inappropriate level of innovation or use of new technologies. In addition, the effect of exogenous factors on productivity is analysed using the Kruskal-Wallis (KW) test, finding that productivity levels were affected by the quality of the influent water and the size of the plants, but not by the other factors considered.     

Continuous electrochemical treatment of phenolic wastewater in a tubular reactor

The electrochemical treatment of phenolic wastewater in a continuous tubular reactor, constructed from a stainless steel tube with a cylindrical carbon anode at the centre, was investigated in this study, being first in literature. The effects of residence time on phenol removal was studied at 25 degrees C, 120 g l(-1) electrolyte concentration for 450 and 3100 mg l(-1) phenol feed concentrations with 61.4 and 54.7 mA cm(-2) current densities, respectively. The change in phenol concentration and pH of the reaction medium was monitored in every run and GC/MS analyses were performed to determine the fate of intermediate products formed during the electrochemical reaction in a specified batch run. During the electrolysis mono, di- and tri-substituted chlorinated phenol products were initially formed and consumed along with phenol thereafter mainly by polymerization mechanism. For 10 and 20 min of residence time phenol removal was 56% and 78%, respectively, with 450 mg l(-1) phenol feed concentration and above 40 min of residence time all phenol was consumed within the column. For 1, 1.5, 2 and 3h of residence time, phenol removal achieved was 42%, 71%, 81% and 98%, respectively, at 3100 mg l(-1) phenol feed concentration. It is noteworthy that more than 95% of the initial phenol was converted into a non-passivating polymer without hazardous end products in a comparatively fast and energy-efficient process, being a safe treatment.     

Influence of electric current on bacterial viability in wastewater treatment

Minimizing the influence of electric current on bacterial viability in the electro-technologies such as electrophoresis and electrocoagulation is crucial in designing and operating the electric hybrid wastewater treatment system. In this study the biomass from a membrane bioreactor (MBR) was subjected to constant direct current and the bacterial viability was monitored against electrical intensity, duration as well as the spatial vicinity related to the electrodes. It was found that the bacterial viability was not significantly affected (less than 10% of death percentage) when the applied electric current density (CD) was less than 6.2 A/m² after 4 h. The percentage of live cell dropped by 15% and 29% at CD of 12.3 A/m² and 24.7 A/m², respectively. The pH of electrolytic biomass fluid has shifted to alkaline (from nearly neutral to around pH 10) at CD above 12.3 A/m², which could have been the contributing factor for the bacterial inactivation. The temperature change in the electrolytic media at all current densities during 4 h of experiment was less than 2 °C, thus temperature effects were negligible. Bacteria experienced different micro-environments in the electrochemical reactor. Bacterial cells on the cathode surface exhibited highest death rate, whereas bacteria outside the space between electrodes were the least affected. It was concluded that in an electro-technology integrated wastewater treatment process, sufficient mixing should be used to avoid localized inactivation of bacterial cells.     

Adsorbent obtained from CEPT sludge in wastewater chemically enhanced treatment

Chemically enhanced primary treatment (CEPT) in municipal wastewater treatment is particularly suitable for rapidly growing cities. The focus on CEPT process now might be the cost of chemicals and disposal of chemical sludge. In this study, the potential application of adsorbent made from CEPT sludge in CEPT wastewater treatment was investigated in various conditions, such as the adsorbent dosage, pH, and dosing modes of ferric chloride and adsorbent. It was found that sludge-derived adsorbent was a good way of sludge disposal while enhanced pollutants removal rate and reduced the fresh ferric chloride dosage. With the use of 10.0 mg L⁻¹ of ferric chloride and 0.6 g L⁻¹ of the adsorbent at the first stage simultaneously, the enhanced removal efficiencies of turbidity, UV₂₅₄, COD, TP were 83.3%, 52.3%, 48.8% and 89.0%, respectively. The experiments showed that ferric chloride dose was reduced about 50%. The pH played a significant role in coagulation and adsorption process.