Themistokles D. Lekkas

Comparison of methods for determination of volatile organic compounds in drinking water

Comparison of four methods including liquid-liquid extraction (LLE), direct aqueous injection (DAI), purge and trap (PAT) and head space (HS) were carried out in this work for determination of volatile organic compounds (VOCs) including trihalomethanes (THMs) in drinking water. This comparison is made especially to show the advantages and disadvantages and specifically the different detection limits (DL) that can be obtained for a given type of analysis. LLE is applicable only for determination of the THMs concentrations, while DAI, PAT, HS methods with different DL each of them are applicable for all VOCs, with PAT to be the most sensitive. Sampling apparatus and procedure for all these methods except of PAT are very simple and easy, but possible disadvantages for LLE and DAI are the low sensitivity and especially the detection only of THMs with LLE.

Application of different analytical methods for determination of volatile chlorination by-products in drinking water.

Four analytical methods have been applied for the determination of volatile chlorination by-products in drinking water, based on the following techniques: liquid-liquid extraction-gas chromatography-electron capture detection (LLE-GC-ECD); liquid-liquid extraction-gas chromatography-mass spectrometry (LLE-GC-MS); purge and trap-gas chromatography-mass spectrometry (purge and trap-GC-MS); and headspace-gas chromatography-mass spectrometry (headspace-GC-MS). The compounds studied were trihalomethanes, haloacetonitriles, haloketones, chloral hydrate and chloropicrin. LLE-GC-ECD method proved to be the most sensitive for determination of all compounds studied, followed by LLE-GC-MS. Purge and trap-GC-MS method gave good results in the case of trihalomethanes, but had high detection limits for the other volatile chlorination by-products. Headspace-GC-MS method had acceptable recoveries for trihalomethanes, but the detection limits were higher.

Fate of selected pharmaceuticals and synthetic endocrine disrupting compounds during wastewater treatment and sludge anaerobic digestion

The concentrations of nine emerging contaminants, including pharmaceutically active compounds (PhACs) (ibuprofen, IBF; naproxen, NPX; diclofenac, DCF; ketoprofen, KFN) and endocrine disrupting chemicals (triclosan, TCS; bisphenol, BPA; nonylphenol, NP; nonylphenol monoethoxylate, NP1EO; nonylphenol diethoxylate, NP2EO), were determined in wastewater and sludge samples of two wastewater treatment plants (WWTPs) in Greece. Average concentrations in raw and treated wastewater ranged from 0.39 (KFN) to 12.52 μg L(-1) (NP) and from <LOD (IBF) to 0.80 μg L(-1) (DCF), respectively. A significant part of nonylphenols (NPs) and TCS in influent wastewater was bound to the particulate phase, while PhACs and BPA were mainly detected in the aqueous phase. Removal of target compounds during wastewater treatment ranged between 39% (DCF) and 100% (IBF). Except of DCF and BPA, similar removal efficiencies were observed in both WWTPs and no effect of WWTPs size and operational conditions was noticed. Use of mass balances showed that accumulation on sludge was a significant removal mechanism for NPs and TCS, while biodegradation/biotransformation was the major mechanism for the other compounds. Sampling of raw and digested sludge demonstrated that IBF and NPX are significantly removed (>80%) during anaerobic digestion, whereas removal of EDCs was lower, ranging up to 55% for NP1EO.

Effect of chromium(VI) on bacterial kinetics of heterotrophic biomass of activated sludge.

The effect of hexavalent chromium, Cr(VI), on the maximum specific growth rate, mu(m) and biomass yield, Y(H), of heterotrophic biomass was studied in batch tests conducted under high (= 10) and low (= 1.5) substrate-to-biomass ratios (S0/X0). The effects of sludge age and biomass acclimatization to Cr(VI) on the bacterial kinetics were also studied. The mu(m) values were determined by measuring oxygen uptake rate (OUR) and volatile suspended solids (VSS) increase. Cr(VI) concentrations equal or greater than 10 mg l(-1) inhibited the growth of unacclimatized activated sludge and caused a significant decrease in mu(m) and Y(H) values. The acclimatization of biomass and the selection of a high operating sludge age reduced the inhibitory effect of Cr(VI). At a sludge age of 20 days, Cr(VI) concentrations of <10 mg l(-1) stimulated bacterial growth as evidenced by an increase in both the mu(m) and Y(H) values. Determining mu(m) values by OUR and VSS methods, revealed that the presence of Cr(VI) in unacclimatized biomass caused an inhibitory effect mostly on substrate oxidation, while in acclimatized biomass, anabolic pathways were inhibited more.

Contribution of primary and secondary treatment on the removal of benzothiazoles, benzotriazoles, endocrine disruptors, pharmaceuticals and perfluorinated compounds in a sewage treatment plant

The occurrence and fate of 36 emerging contaminants, belonging to five different classes, (benzotriazoles, BTRs; benzothiazoles, BTHs; perfluorinated compounds, PFCs; non-steroidal anti-inflammatory drugs, NSAIDs and endocrine disruptors, EDCs) were investigated in raw, treated wastewater (both particulate and dissolved phases), and in sludge from a sewage treatment plant (STP) in Athens, Greece. The average concentrations of BTRs, BTHs, NSAIDs and EDCs in raw wastewater ranged between 11 ng L(-1) and 7.27 μg L(-1), while PFCs did not exceed 100 ng L(-1). In dewatered sludge, the average concentrations ranged between 0.8 ng g(-1) dw (perfluorohexanoic acid, PFHxA) and 3895 ng g(-1) dw (nonylphenol, NP). The distribution of emerging contaminants between particulate and dissolved phase was different among the compounds. BTRs and BTHs showed lower solid-liquid distribution coefficients (Kd) than all other compounds. For 9 over the 27 compounds detected in influents, the removal efficiency was higher than 70%, while the others either were removed to a lesser extent or detected at higher concentrations in effluents. Based on this, advanced treatment processes should be applied in the future for achieving adequate emerging contaminants removal in STPs. Regarding removal mechanisms, almost 60% of BTRs and 30 to 75% of BTHs were removed in bioreactors, while the contribution of primary and secondary clarifiers was of minor importance. Sorption to primary sludge was a significant mechanism affecting EDCs fate in STP.

Effects of chromium (VI) addition on the activated sludge process.

The effect of hexavalent chromium, Cr(VI), addition on various operating parameters of activated sludge process was evaluated. To accomplish this, two parallel lab-scale continuous-flow activated sludge plants were operated. One was used as a control plant, while the other received Cr(VI) concentrations equal to 0.5, 1, 3 and 5 mgl(-1). Cr(VI) concentrations of 0.5 mgl(-1) caused significant inhibition of the nitrification process (up to 74% decrease in ammonia removal efficiency). On the contrary, the effect of Cr(VI) on organic substrate removal was minor for concentrations up to 5 mgl(-1), indicating that heterotrophic microorganisms are less sensitive to Cr(VI) than nitrifiers. Activated sludge floc size and structure characterization showed that Cr(VI) concentrations higher than 1 mgl(-1) reduced the filaments abundance, causing the appearance of pin-point flocs and free-dispersed bacteria. Additionally, the variability of protozoa and rotifers was reduced. As a result of disperse growth, effluent quality deteriorated, since significant amounts of suspended solids escaped with the effluent. Termination of Cr(VI) addition led to a partial recovery of the nitrification process (up to 57% recovery). Similar recovery signs were not observed for activated sludge floc size and structure. Finally, shock loading to the control plant with 5 mgl(-1) Cr(VI) for 2 days resulted in a significant inhibition of the nitrification process and a reduction in filamentous microorganisms abundance.

Determination of volatile organic compounds in surface waters and treated wastewater in Greece

The occurrence of volatile organic compounds (VOCs) was studied in river water, lake water, seawater and treated wastewater in Greece from October 1998 to September 1999. The determination of 41 VOCs was performed with a Purge and Trap-Gas Chromatography-Mass Spectrometry method. Samples were collected seasonally from 10 rivers, seven lakes, three gulfs and four wastewater treatment plants. In surface water samples, 15 VOCs were detected. In wastewater samples, occurrence of 31 VOCs was observed. The results suggest that not only agricultural and industrial activity within the Greek territory, but also transboundary pollution deriving from neighbouring countries consist important sources of VOCs in surface waters of Greece. However, the measured concentrations did not in any case exceed the guideline values proposed by the EC.

The role of natural organic matter during formation of chlorination by-products : A review

The role of natural organic matter (NOM) in chlorination by-product formation in drinking water is complex, since characteristics of NOM and its behavior during water treatment have not yet been clearly identified. Different approaches have been applied to characterize NOM, with the objective to investigate the mechanisms of its reactions with chlorine. In this way, formation of by-products, which may have adverse health effects on humans, could be minimized. These approaches are summarized in the present review. Efforts to correlate NOM properties with formation of chlorination by-products and conclusions resulting from chlorination of humic and fulvic acid as well as raw water are also discussed.

DBP levels in chlorinated drinking water: effect of humic substances.

Chlorination is the most widely used technique for disinfection of drinking water. A consequence of chlorination is the formation of Disinfection By-Products (DBPs). The formation of DBPs in drinking water results from the reaction of chlorine with naturally occurring organic materials, principally humic and fulvic acids. This paper focuses on the effect of humic substances on the formation of twenty-four compounds belonging to different categories of DBPs. This investigation was conducted in two water treatment plants in Greece, Menidi and Galatsi, from July 1999 to April 2000. Humic substances were determined by the diethylaminoethyl (DEAE) method with subsequent UV measurement. The techniques used for the determination of DBPs were liquid-liquid extraction, gas chromatography and mass spectrometry. The concentrations of DBPs were generally low. Total trihalomethanes (TTHMs) ranged from 5.1 to 24.6 μg L-1, and total haloacetic acids (HAAs) concentration ranged from 8.6 to 28.4 μg L-1, while haloaketones (HKs) and chloral hydrate (CH) occurred below 1 μg L-1. The content of humic substances was found to influence the formation of DBPs and especially TTHMs, trichloroacetic acid (TCA), dibromoacetic acid (DBA), CH, 1,1-dichloropropanone (1,1-DCP) and 1,1,1-trichloropropanone (1,1,1-TCP). Seasonal variation of TTHMs and HAAs generally followed that of humic substances content with peaks occurring in autumn and spring. The trends of 1,1-DCP, 1,1,1-TCP and CH formation seemed to be in contrast to TTHMs and HAAs. Trends of formation of individual compounds varied in some cases, probably due to influence of parameters other than humic substances content. Statistical analysis of the results showed that the concentrations of TTHMs, CH, 1,1-DCP, 1,1,1-TCP, TCA and DBA are strongly affected from humic substances content (at 0.01 confidence level). The opposite is true for dichloroacetic acid (DCA) concentration. Humic substances also vary to a statistically significant degree during different months, as well as the concentrations of TTHMs, CH, 1,1-DCP, 1,1,1-TCP, TCA and DCA. The variance of DBA was not statistically significant. Regarding the effect of sampling station, humic substances content showed no statistically significant difference between the two raw water sources studied.

Chromium species behaviour in the activated sludge process.

The purpose of this research was to compare trivalent chromium (Cr(III)) and hexavalent chromium (Cr(VI)) removal by activated sludge and to investigate whether Cr(VI) reduction and/or Cr(III) oxidation occurs in a wastewater treatment system. Chromium removal by sludge harvested from sequencing batch reactors, determined by a series of batch experiments, generally followed a Freundlich isotherm model. Almost 90% of Cr(III) was adsorbed on the suspended solids while the rest was precipitated at pH 7.0. On the contrary, removal of Cr(VI) was minor and did not exceed 15% in all experiments under the same conditions. Increase of sludge age reduces Cr(III) removal, possibly because of Cr(III) sorption on slime polymers. Moreover, the decrease of suspended solids concentration and the acclimatization of biomass to Cr(VI) reduced the removal efficiency of Cr(III). Batch experiments showed that Cr(III) cannot be oxidized to Cr(VI) by activated sludge. On the contrary, Cr(VI) reduction is possible and is affected mainly by the initial concentration of organic substrate, which acts as electron donor for Cr(VI) reduction. Initial organic substrate concentration equal to or higher than 1000 mgl(-1) chemical oxygen demand permitted the nearly complete reduction of 5 mgl(-1) Cr(VI) in a 24-h batch experiment. Moreover, higher Cr(VI) reduction rates were obtained with higher Cr(VI) initial concentrations, expressed in mg Cr(VI) g(-1) VSS, while decrease of suspended solids concentration enhanced the specific Cr(VI) reduction rate.