Removal of pathogens from greywater using green roofs combined with chlorination

Environmental Science and Pollution Research - Greywater is an important alternative water resource which could be treated and reused in buildings, reducing the freshwater demand in drought...     

Chemical solutions for greywater recycling

Greywater recycling is now accepted as a sustainable solution to the general increase of the fresh water demand, water shortages and for environment protection. However, the majority of the suggested treatments are biological and such technologies can be affected, especially at small scale, by the variability in strength and flow of the greywater and potential shock loading. This investigation presents the study of alternative processes, coagulation and magnetic ion exchange resin, for the treatment of greywater for reuse. The potential of these processes as well as the influence of parameters such as coagulant or resin dose, pH or contact time were investigated for the treatment of two greywaters of low and high organic strengths. The results obtained revealed that magnetic ion exchange resin and coagulation were suitable treatment solutions for low strength greywater sources. However, they were unable to achieve the required level of treatment for the reuse of medium to high strength greywaters. Consequently, these processes could only be considered as an option for greywater recycling in specific conditions that is to say in case of low organic strength greywater or less stringent standards for reuse.     

Total staphylococci as performance surrogate for greywater treatment

Faecal indicator bacteria (FIB) are commonly used as water quality indicators; implying faecal contamination and therefore the potential presence of pathogenic enteric bacteria, viruses, and protozoa. Hence in wastewater treatment, the most commonly used treatment process measures (surrogates) are total coliforms, faecal coliforms, Escherichia coli (E. coli), and enterococci. However, greywater potentially contains skin pathogens unrelated to faecal load, and E. coli and other FIB may grow within greywater unrelated to pathogens. Overall, FIB occurs at fluctuating and relatively low concentrations compared to other endogenous greywater bacteria affecting their ability as surrogates for pathogen reduction. Therefore, unlike municipal sewage, FIB provides a very limited and unreliable log-reduction surrogate measure for on-site greywater treatment systems. Based on our recent metagenomic study of laundry greywater, skin-associated bacteria such as Staphylococcus, Corynebacterium, and Propionibacterium spp. dominate and may result in more consistent treatment surrogates than traditional FIB. Here, we investigated various Staphylococcus spp. as potential surrogates to reliably assay over 4-log₁₀ reduction by the final-stage UV disinfection step commonly used for on-site greywater reuse, and compare them to various FIB/phage surrogates. A collimated UV beam was used to determine the efficacy of UV inactivation (255, 265 and 285 nm) against E. coli, Enterococcus faecalis, E. faecium, E. casseliflavus, Staphylococcus aureus, and S. epidermidis. Staphylococcus spp. was estimated by combining the bi-linear dose-response curves for S. aureus and S. epidermidis and was shown to be less resistant to UV irradiation than the other surrogates examined. Hence, a relative inactivation credit is suggested; whereas, the doses required to achieve a 4 and 5-log₁₀ reduction of Staphylococcus spp. (13.0 and 20.9 mJ cm^?2, respectively) were used to determine the relative inactivation of the other microorganisms investigated. The doses required to achieve a 4 and 5-log₁₀ reduction of Staphylococcus spp. resulted in a log₁₀ reduction of 1.4 and 4.1 for E. coli, 0.8 and 2.8 for E. faecalis, 0.8 and 3.6 for E. casseliflavus and 0.8 and 1.2 for MS2 coliphage, respectively. Given the concentration difference of Staphylococcus spp. and FIB (3 to 5-log₁₀ higher), we propose the use of Staphylococcus spp. as a novel endogenous performance surrogate to demonstrate greywater treatment performance given its relatively high and consistent concentration and therefore ability to demonstrate over 5-log₁₀ reductions.     

Harvesting of microalgae biomass from the phycoremediation process of greywater

The wide application of microalgae in the field of wastewater treatment and bioenergy source has improved research studies in the past years. Microalgae represent a good source of biomass and bio-products which are used in different medical and industrial activities, among them the production of high-valued products and biofuels. The present review focused on greywater treatment through the application of phycoremediation technique with microalgae and presented recent advances in technologies used for harvesting the microalgae biomass. The advantages and disadvantages of each method are discussed. The microbiological aspects of production, harvesting and utilization of microalgae biomass are viewed.     

Formation of chloroform by aqueous chlorination of organic compounds.

Thirty organic compounds were selected to investigate their chloroform formation characteristics during chlorination with sodium hypochlorite at pH-values 7.0 and 8.0. These experiments were conducted under conditions similar to those applied on the chlorination of raw water. The results indicated that the chloroform concentrations occurred by the all tested compounds was in the ppm range. The maximum levels of chloroform (11-13 mg/l) were determined during the reaction of resorcinol and phloroglucinol at pH-value 8.0.     

Gas phase naphthalene chlorination

Chlorination of naphthalene by Cl atoms has been studied in the gas phase. The chlorinating agent was produced by γ-radiolysis of tetrachloromethane. At low conversions only monosubstituted products are observed. Both isomers are formed, the yield of 1-chloronaphthalene exceeding that one of its isomer. The extent of the addition reaction increases with the temperature. The relative Arrhenius plot of observed rate constants is linear over the temperature range investigated (60–120 °C) and its slope corresponds to a difference of 11.0 kJ/mol between the activation energies of 2-chloronaphthalene and 1-chloronaphthalene.     

Peracetic acid disinfection: a feasible alternative to wastewater chlorination.

The paper summarizes the results of a bench-scale study to evaluate the feasibility of using peracetic acid (PAA) as a substitute for sodium hypochlorite both for discharge into surface water and for agricultural reuse. Trials were carried out with increasing doses (1, 2, 3, 5, 10, and 15 mg/L) and contact times (6, 12, 18, 36, 42, and 54 minutes) to study disinfectant decay and bacterial removal and regrowth, using fecal coliform and Escherichia coli (E. coli) as process efficiency indicators. Peracetic acid decay kinetics was evaluated in tap water and wastewater; in both cases, PAA decays according to first-order kinetics with respect to time, and a correlation was found between PAA oxidative initial consumption and wastewater characteristics. The PAA disinfection efficiency was correlated with operating parameters (active concentration and contact time), testing different kinetic models. Two data groups displaying a different behavior on the basis of initial active concentration ranges (1 to 2 mg/L and 5 to 15 mg/L, respectively) can be outlined. Both groups had a "tailing-off" inactivation curve with respect to time, but the second one showed a greater inactivation rate. Moreover, the effect of contact time was greater at the lower doses. Hom's model, used separately for the two data groups, was found to best fit experimental data, and the disinfectant active concentration appears to be the main factor affecting log-survival ratios. Moreover, the S-model better explains the initial resistance of E. coli, especially at low active concentrations (< 2 mg/L) and short contact times (< 12 minutes). Microbial counts, performed by both traditional methods and flow cytometry, immediately and 5 hours after sample collection (both with or without residual PAA inactivation), showed that no appreciable regrowth took place after 5 hours, neither for coliform group bacteria, nor for total heterotrophic bacteria.     

Catalytic destruction of chloramine to nitrogen using chlorination and activated carbon--case study.

The paper presents the results of laboratory and pilot studies on the removal of chloramine from potable water using chlorination with a less-than-breakpoint dosage of chlorine, followed by treatment with catalytic activated carbon. The effect of the chlorine-to-nitrogen ratio, temperature, and carbon contact time were investigated to optimize conditions for chloramines removal and minimize the production of ammonia. Results demonstrated that prechlorination of water, followed by treatment with catalytic activated carbon, can degrade monochloramine to nitrogen gas as a main product. For all chlorine-to-ammonia ratios studied, the observed rates of monochloramine removal were higher at a temperature of 20 degrees C than they were at 5 degrees C. Generation of ammonia was slightly higher at the lower temperature. However, at both temperatures, practically all monochloramine was destroyed, and only insignificant amounts of ammonia were formed when a chlorine-to-ammonia ratio of 7:1 was applied. The described method is simple and cost-effective, because it eliminates the requirement of removal of ammonia, typically formed during the treatment of chloramines with activated carbon.     

Effects of chlorination on the adhesion strength and deflocculation of activated sludge flocs.

A side effect of the application of chlorine for controlling filamentous bulking is deflocculation of floc-forming bacteria, which may cause unacceptable effluent deterioration depending on dosing. It was assumed that chlorine may adversely affect the adhesion ability of floc bacteria, promoting their erosion in shear flow. The effect of chlorination on the strength of activated sludge flocs was investigated. The adhesion-erosion (AE) model developed by Mikkelsen and Keiding was used to interpret results from deflocculation tests with varying shear and solids concentration. The AE model yields the adhesion enthalpy (deltaHG/R) of cells in sludge flocs and parameters from the model were used to quantify the sludge in terms of floc strength. Two activated sludges with different initial characteristics were studied. The resulting model parameters showed that the AE model was suitable for quantifying the bond energy of particles to the activated sludge exposed to chlorine. For one activated sludge, adhesion of cells was largely unaffected by the applied chlorine doses. A second sludge showed reduced adhesion strength with chlorine, leading to increasing deflocculation. The simple batch test and AE model proved valuable for assessing the effect of chlorination on the flocs in activated sludge. By use of these procedures, it is possible to determine acceptable chlorine dosing to avoid excessive deflocculation and effluent deterioration.     

Unusual products of the aqueous chlorination of atenolol

The reaction of the drug atenolol with hypochlorite under conditions that simulate wastewater disinfection was investigated. The pharmaceutical reacted in 1h yielding three products that were separated by chromatographic techniques and characterized by spectroscopic features. Two unusual products 2-(4-(3-(chloro(2-chloropropan-2-yl)amino)-2-hydroxypropoxy)phenyl) acetamide and 2-(4-(3-formamido-2-hydroxypropoxy)phenyl) acetamide were obtained along with 2-(4-hydroxyphenyl) acetamide. When the reaction was stopped at shorter times only 2-(4-(3-amino-2-hydroxypropoxy)phenyl) acetamide and the dichlorinated product were detected. Tests performed on the seeds of Lactuca sativa show that chlorinated products have phytotoxic activity.     

Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene

The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C₂ through C₈ organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene.     

Chloroperoxidase-mediated chlorination of aromatic groups in fulvic acid

The aim of the present study is to investigate whether exo-enzymatically mediated chlorination of fulvic acid (FA) results in the formation of chlorinated groups within the macromolecules which correspond to those which were previously detected in soil and surface water samples. The chlorination was carried out by exposing FA to a commercial chloroperoxidase (CPO) in the presence of chloride and hydrogen peroxide. The exposed FA was then chemically degraded using an oxidative technique and finally analysed for four different aromatic groups and their chlorinated analogues. The particular aromatic groups included were the methyl esters of 4-ethoxybenzoic acid, 3-methoxy-4-ethoxybenzoic acid, 3,4-diethoxybenzoic acid, and 3,5-dimethoxy-4-ethoxybenzoic acid, along with their mono- and dichlorinated analogues. Prior to the chemical degradation procedure, the FA was analysed for AOX (adsorbable organic halogens) and chlorinated acetic acids. The original FA contained 1.4 mg Cl(org) g(-1) and detectable amounts of two chlorinated aromatic groups. After exposure to the enzyme, the concentration of AOX increased to 44.3 mg Cl(org) g(-1) and detectable amounts of four chlorinated aromatic groups as well as di- and trichloroacetic acid were found.     

Formation of PCDDs and PCDFs by the chlorination of water

Two samples of tab water and double distilled water were chlorinated using chlorine gas. A series of PCDFs could be identified from these experiments, however no PCDDs could be found. The two water samples gave very similar isomeric patterns ( . . tetra-CDFs), however the congener profile (Cl₄ --- Cl₈) was different. These experiments indicate that all products formed by chlorination reactions are potentially contaminated by PCDFs by a specific “chlorine pattern”.     

Identification and behavior of reaction products formed by chlorination of ethynylestradiol

Six products were formed by reaction of ethynylestradiol (EE2) with sodium hypochlorite in buffered solutions. 4-Chloroethynylestradiol (4-ClEE2) and 2,4-dichloroethynylestradiol (2,4-diClEE2) were identified as the two major reaction products, using preparative HPLC, MS, and NMR. When EE2 reacted with chlorine at different pHs (pH 5, 7, and 9) or chlorine concentrations (0.2, 1, 2, and 5 mmol/l, corresponding to molar ratios to EE2, 1, 5, 10, and 25, respectively), the formation of 4-ClEE2 and 2,4-diClEE2 was observed under the above conditions, and the highest yields were 20 and 52 mol%, respectively. EE2 was consumed almost completely within 5 min of chlorination by addition of chlorine of more than 1 mmol/l (molar ratio to EE2, 5). On the other hand, the two products existed in highly chlorinated solutions after 60 min (4ClEE2, 1-6 mol%; 2,4-diClEE2, 3-25 mol%). The estrogenic activities of 4-ClEE2 by estrogen receptor alpha or beta binding assay were similar to those of the parent EE2, and the activities of 2,4-diClEE2 were lower about 10 times.     

Formation of volatile halogenated by-products during chlorination of isoproturon aqueous solutions

The present paper deals with the formation of volatile halogenated by-products (POX) during the chlorination (160 mg/l) of aqueous solutions of the herbicide isoproturon (40 mg/l). Chlorination reactions have been carried out over 48 h, at ambient temperature, at two pHs (6 and 9) and in the presence or not of bromide ions (80 mg/l). The main results obtained have been as follows: (1) in the presence of bromide, isoproturon degradation is rather fast and it results affected by pH, complete isoproturon degradation is achieved within 1 and 15 min at pH 6 and 9, respectively; (2) in the absence of bromide herbicide degradation is slow (complete degradation is achieved within 180 min) and it is not affected by pH; (3) at pH 6, regardless of the presence of bromide, the maximum amount of POX formed is low (approximately 15 micromol X-/l) and remains constant during the reaction; (4) at pH 9 the amount of POX formed is far greater and continuously increases during the reaction, reaching a value of about 110 micromol X-/l after 48 h; (5) two different groups of by-products have been identified by solid phase micro extraction (SPME)-gas chromatography (GC)-mass spectrometry (MS) for the reactions carried out with or without bromide; among them, aliphatic as well as aromatic by-products containing chlorine, bromine or both halogens are present even though the most abundant are halogenated-methane derivatives (haloforms); pH value affects the amount of these by-products but does not modify their chemical nature.     

Ability of Indian pennywort Bacopa monnieri (L.) Pennell in the phytoremediation of sewage (greywater)

Environmental Science and Pollution Research - The freely and abundantly available amphibious plant Indian pennywort Bacopa monnieri (L.) Pennell was able to phytoremediate sewage (greywater)...     

The formation of chlorodibenzo-p-dioxins by air oxidation and chlorination of bituminous coal

A well characterized bituminous coal was subjected to high temperature air oxidation and chlorination. After an extensive cleanup procedure, the reaction products were analyzed for chlorinated dibenzo-p-dioxins by gas chromatography-mass spectrometry. Substantial quantities of chlorodibenzo-p-dioxins, some of which are known to be highly toxic, were observed with chlorination by hydrogen chloride and chlorine gas.     

Feed-forward dose control of wastewater chlorination using on-line pH and ORP titration

In this study, a simple automatic pH-ORP titration device was developed for identifying the various ammonia concentrations and chlorine dose requirements for wastewater chlorination by identifying the peaks in the ORP-slope profiles and knees/valleys in the pH profiles. In addition, breakpoint chlorination experiments have shown that the ORP values at the monochloramine humps and breakpoints are linearly correlated with the ammonia concentrations. Therefore, a feed-forward control strategy, based on the chlorine/ammonia weight ratio (Cl/N), is proposed in this paper, to control the chlorine doses for a continuous wastewater chlorination experiment in a laboratory-scale reactor. The result of this continuous wastewater chlorination experiment has shown that the pH-ORP titration was able to precisely determine the variations of ammonia concentrations in the chlorination influent. Under this control strategy, effective and stable disinfection efficiencies in terms of total coliform count were obtained.     

Precursors and nitrogen origins of trichloronitromethane and dichloroacetonitrile during chlorination/chloramination

The formation of trichloronitromethane (TCNM) and dichloroacetonitrile (DCAN) was investigated during chlorination and chloramination of 31 organic nitrogen (org-N) compounds, including amino acids, amines, dipeptides, purines, pyrimidones and pyrroles. Tryptophan and alanine generated the greatest amount of TCNM during chlorination process and asparagine and tyrosine yielded the highest amount of TCNM during chloramination process. Tryptophan, tyrosine, asparagine, and alanine produced more DCAN than other org-N compounds regardless of chlorination or chloramination. TCNM and DCAN formation was higher by chlorination than by chloramination. NH₂Cl:org-N molar ratios, reaction time, and pH affected N-DBPs formation in varying degrees. TCNM and DCAN yields were usually high during chloramination of tyrosine, asparagine, and methylpyrrole under the following reaction conditions: NH₂Cl:org-N molar ratios greater than 10, reaction time for 1 d, and at pH 7.2. NH₂Cl as a major nitrogen origin in TCNM and DCAN was confirmed via labeled ¹⁵N-monochloramine during chloramination of tyrosine, asparagine and methylpyrrole. In contrast, the majority of nitrogen in TCNM originated from glycine, and that in DCAN originated from pyrrole. Based on the intermediates identified by gas chromatography/mass spectrometry (GC/MS), a pathway scheme was proposed for TCNM and DCAN formation.     

Modeling the formation of chlorination by-products in river waters with different quality

Water chlorination results in formation of a variety of organic compounds, known as chlorination by-products (CBPs), mainly trihalomethanes (THMs) and haloacetic acids (HAAs). Factors affecting their concentrations have been found to be organic matter content of water, pH, temperature, chlorine dose, contact time and bromide concentration, but the mechanisms of their formation are still under investigation. Within this scope, chlorination experiments have been conducted with river waters from Lesvos island, Greece, with different water quality regarding bromide concentration and organic matter content. The factors studied were pH, time and chlorine dose. The determination of CBPs was carried out by gas chromatography techniques. Statistical analysis of the results was focused on the development of multiple regression models for predicting the concentrations of total trihalomethanes and total HAAs based on the use of pH, reaction time and chlorine dose. The developed models, although providing satisfactory estimations of the concentrations of the CBPs, showed lower correlation coefficients than the multiple regression models developed for THMs only during previous study. It seems that the different water quality characteristics of the two river waters in the present study is responsible for this phenomenon. The results indicate that under these conditions the formation of THMs and HAAs in water has a more stochastic character, which is difficult to be described by the conventional regression techniques.