Estimating DOC regime in a wastewater treatment plant by UV deconvolution

A UV-deconvolution method was modified, and applied to estimation of dissolved organic carbon (DOC) along a municipal wastewater treatment plant (WWTP) in Catalonia, Spain. One grab sample was taken every 2h at four sampling points, for 1 week (336 samples), in order to characterise day/night and weekday/weekend DOC regimes along the plant. Samples were centrifuged before DOC determination or estimation. Four components were selected for describing wastewater composition and spectra. Reference spectra for these components were taken from the literature and proved to correctly explain the sample spectra. A two-step deconvolution method was developed, which avoided negative nitrate coefficients while keeping deconvolution error low. The calibration file for DOC estimation was determined by analysing DOC and acquiring UV spectra from 48 samples. DOC values were correlated to UV spectra by multiple linear regression. Determination coefficient and standard error were comparable to the values found in the literature. In raw or diluted samples with an absorbance between 2.0 and 2.5, DOC was probably underestimated by the method. This points to some nonlinearity for absorbances above 2.0, rather than the 2.5 limit suggested by the original method. DOC calculation through UV deconvolution allowed for the estimation of DOC regime along the WWTP. Time bands for higher and lower DOC concentrations were determined and characterised at each sampling point, for weekdays and the weekend. Except for the plant effluent, clear time bands were found. In effluent, DOC was always low, and very small oscillations were detected, due to DOC removal and intense mixing in the biological process. DOC profiles at each point are discussed in this paper. The modified deconvolution method has proved to be an accurate and efficient technique for estimating DOC of a large number of raw and diluted samples.     

Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation

This work reports a systematic survey of over seventy individual pollutants in a Sewage Treatment Plant (STP) receiving urban wastewater. The compounds include mainly pharmaceuticals and personal care products, as well as some metabolites. The quantification in the ng/L range was performed by Liquid Chromatography-QTRAP-Mass Spectrometry and Gas Chromatography coupled to Mass Spectrometry. The results showed that paraxanthine, caffeine and acetaminophen were the main individual pollutants usually found in concentrations over 20 ppb. N-formyl-4-amino-antipiryne and galaxolide were also detected in the ppb level. A group of compounds including the beta-blockers atenolol, metoprolol and propanolol; the lipid regulators bezafibrate and fenofibric acid; the antibiotics erythromycin, sulfamethoxazole and trimethoprim, the antiinflammatories diclofenac, indomethacin, ketoprofen and mefenamic acid, the antiepileptic carbamazepine and the antiacid omeprazole exhibited removal efficiencies below 20% in the STP treatment. Ozonation with doses lower than 90 μM allowed the removal of many individual pollutants including some of those more refractory to biological treatment. A kinetic model allowed the determination of second order kinetic constants for the ozonation of bezafibrate, cotinine, diuron and metronidazole. The results show that the hydroxyl radical reaction was the major pathway for the oxidative transformation of these compounds.     

Improvement of organics removal by bio-ceramic filtration of raw water with addition of phosphorus

The purpose of this study was to investigate the effect of phosphorus addition on biological pretreatment of raw water. Experiments were conducted in pilot-scale bio-ceramic filters with raw water from a reservoir located in Beijing, China. The results demonstrated that phosphorus was the limiting nutrient for bacterial growth in the raw water investigated in this study. The measured values of bacterial regrowth potential (BRP) and biodegradable dissolved organic carbon (BDOC) of the raw water increased by 50-65% and 30-40% with addition of 50 microg of PO4(3-)-PL(-1), respectively. Addition of 25 microg of PO4(3-)-PL(-1) to the influent of bio-ceramic filter enhanced the percent removal of organics by 4.6, 5.7 and 15 percentage points in terms of COD(Mn), TOC and BDOC, respectively. Biomass in terms of phospholipid content increased by 13-22% and oxygen uptake rate (OUR) increased by 35-45%. The ratio of C:P for bacteria growth was 100:1.6 for the raw water used in this study. Since change of phosphorus concentrations can influence the performance of biological pretreatment and the biological stability of drinking water, this study is of substantial significance for waterworks in China. The role of phosphorus in biological processes of drinking water should deserve more attention.     

臭氧-活性炭组合工艺在东南区水厂深度处理中的应用

目前福州市区各自来水厂采用的为常规的水处理工艺,为了消除水源水质对供水水质造成的突变性、无法预测性的影响,本文介绍了在福州东南区水厂原有处理工艺基础上增加臭氧-活性炭工艺的应用情况,并反映出其对提高水厂运行稳定性的良好效果。     

Removal of biodegradable dissolved organic carbon in a water treatment plant

A new scheme of treatment has been developed in the water treatment plant of Ivry-sur-Seine near Paris. This treatment consists of a pretreatment of preozonization, contact coagulation, coagulation on a filter, slow sand filtration, ozonization and GAC filtration. We have tested the efficiency of this new line of treatment for the removal of BDOC and have attempted to correlate the results with the removal of organic matter (global parameters). Results show a very good efficiency of slow sand filtration and we think that this treatment step allows production of a biologically stable water.     

Decreasing DOC trends in soil solution along the hillslopes at two IM sites in southern Sweden--geochemical modeling of organic matter solubility during acidification recovery

Numerous studies report increased concentrations of dissolved organic carbon (DOC) during the last two decades in boreal lakes and streams in Europe and North America. Recently, a hypothesis was presented on how various spatial and temporal factors affect the DOC dynamics. It was concluded that declining sulphur deposition and thereby increased DOC solubility, is the most important driver for the long-term DOC concentration trends in surface waters. If this recovery hypothesis is correct, the DOC levels should increase both in the soil solution as well as in the surrounding surface waters as soil pH rises and the ionic strength declines due to the reduced input of SO₄²⁻ ions. In this project a geochemical model was set up to calculate the net humic charge and DOC solubility trends in soils during the period 1996-2007 at two integrated monitoring sites in southern Sweden, showing clear signs of acidification recovery. The Stockholm Humic Model was used to investigate whether the observed DOC solubility is related to the humic charge and to examine how pH and ionic strength influence it. Soil water data from recharge and discharge areas, covering both podzols and riparian soils, were used. The model exercise showed that the increased net charge following the pH increase was in many cases counteracted by a decreased ionic strength, which acted to decrease the net charge and hence the DOC solubility. Thus, the recovery from acidification does not necessarily have to generate increasing DOC trends in soil solution. Depending on changes in pH, ionic strength and soil Al pools, the trends might be positive, negative or indifferent. Due to the high hydraulic connectivity with the streams, the explanations to the DOC trends in surface waters should be searched for in discharge areas and peat lands.     

Development of biological filter as tertiary treatment for effective nitrogen removal: Biological filter for tertiary treatment

A biological filtration process applicable to tertiary treatment of sewage for effective nitrogen removal was developed. It consisted of a nitrification filter (Filter 1) and/or a polishing filter with anoxic and oxic parts (Filter 2). A pilot plant set at a municipal sewage treatment plant was operated for 525 d with feed of real sewage. The maximum apparent nitrification rate in Filter 1 in winter was 0.54 kg N/m3- filter-bed d. In Filter 2, the maximum denitrification capacity was 4 kg N/m3 filter-bed d) in winter. SS was stably removed and high transparency water was obtained. The target water quality (SS, BOD, and T-N5 mg/L) was accomplished in winter with the LV of 202 m/d in Filter 2, which corresponds to 0.24 h of HRT. These results proved that this process is compact, stable, convenient to install, and cost effective to build and operate as tertiary treatment to remove nitrogen effectively.     

Artificial groundwater treatment: biofilm activity and organic carbon removal performance

The artificial recharge of sand aquifers with raw source waters is a means both explored and utilised by many water utilities to meet the future potable water demands for increasing urban populations. The microbial ecology within these systems is however, poorly understood, as is the role that microbial biofilms play in the quality of finished water. Knowledge of the ability of biofilm bacteria to metabolise natural organic matter (NOM) is limited, particularly in respect to the degradation of normally recalcitrant hydrophilic and hydrophobic humic acid fractions by sessile and planktonic microbial consortia within sand aquifer systems. To simulate the artificial recharge of sand aquifers that were proposed for the Greater Stockholm Area, four separate 4 m deep sand columns were fed raw lake water and examined over a 45-week study period. The simulated aquifer system (hydraulic retention time 9-16 h) demonstrated the removal of total organic carbon (TOC) (10+/-5%), direct total counts (DTC) of bacteria (74+/-11%), heterotrophic plate count (HPC) bacteria (87+/-5%) and assimilable organic carbon (AOC) (87+/-5%), thereby fulfilling an important barrier function, except for the removal of TOC. Hydrophilic humic acid fractions were more readily metabolised by microbiota (HPC and EUB338-positive cells) harvested from the raw source water (SSM-W), whilst hydrophobic humic acid fractions promoted higher activity by microbiota harvested from the sand matrix (SSM-S). The apparent low activity demonstrated by biofilm microbiota (approximately 40% and 25% of DTC were positive to EUB338 probing for sand matrix and slide biofilms, respectively) could be attributed to the highly recalcitrant nature of the organic loads, whilst at the same time explain the poor removal of TOC. Following nutrient activation (by the PAC assay) nonetheless, a 3-fold increase in the percentage of EUB-positive bacteria was observed on glass slides. Furthermore, the incubation of SSM-S with R2A increased probe-active cells from 57+/-8% to 75+/-7% of DTC and at the same time increased SSM-W from 38+/-8% to 50+/-10%. Whilst these results may imply a good potential for the biological treatment of water by shallow sand aquifers, further work should address the poor removal of TOC observed in this study.     

The effect of ozonation on natural organic matter removal by alum coagulation

Natural organic matter (NOM) was extracted from a moderately colored, eutrophic surface water source (Forge Pond, Granby, MA), and fractionated into quasi-homogeneous fractions. Fulvic acid (FA) and hydrophilic neutrals (HN) were the two most abundant NOM fractions that were isolated. Adsorption affinity of the isolated NOM fractions on preformed aluminum hydroxide flocs increased with increase in specific organic charge of the fractions, except for the two most highly charged fractions, FA and hydrophilic acids (HAA), which showed less adsorption affinity than expected based on their specific organic charge. Prior ozonation of FA and HN fractions resulted in a decline and an increase, respectively, in their adsorption affinity on aluminum hydroxide surface. Prior ozonation of Forge Pond raw water resulted in a progressive decline in dissolved organic carbon (DOC) removal by alum coagulation with increase in ozone dose. It appeared that ozone applied to raw water reacted preferentially with the humic fraction of NOM, resulting in the detrimental effects of ozonation on subsequent NOM removal by alum coagulation being magnified. Forge Pond raw water was pre-coagulated to remove humic substances. Ozonation of the pre-coagulated water demonstrated the beneficial effects of ozonation on the removal of non-humic NOM through alum coagulation. A strategy for staged coagulation with intermediate ozonation was proposed for waters containing both humic and non-humic NOM for maximum DOC and specific UV absorbance at 254nm (SUVA) removal.     

The effect of humic acids on nitrobenzene oxidation by ozonation and O3/UV processes

Three types of commercially available humic acids from different sources were used to simulate natural organic matter in water for the investigation of nitrobenzene oxidation by ozonation and O(3)/UV. Despite the structural differences among the Fluka, Aldrich and Suwanee River humic acids as reflected by the UV absorptivity, their effects on nitrobenzene removal rate was observed to be similar for the two processes. Removal rate of nitrobenzene was hindered by the addition of humic acids in ozonation as well as in O(3)/UV processes. However, the hindrance by the humic acids was more pronounced in O(3)/UV as compared to the ozonation process. The effect of humic acid in O(3)/UV was primarily a UV light screening. Addition of humic acids above a certain concentration did not cause any further retardation on nitrobenzene removal rate by ozonation and O(3)/UV.Accumulation of hydrogen peroxide as well as probable formation of peroxy radicals in the solutions might induce chain promoting reactions to produce hydroxyl radical during the nitrobenzene oxidation. For waters containing high levels of humic acid, ozonation alone might be as effective as O(3)/UV process for the removal of nitrobenzene.     

Integrated ozone and biotreatment of pulp mill effluent and changes in biodegradability and molecular weight distribution of organic compounds

The overall effectiveness of integrating ozonation with biological treatment on the biodegradability enhancement and recalcitrant organic matter (ROM) removal from pulp mill alkaline bleach plant effluent was investigated. Ozonation was performed in a semi-batch bubble column reactor at pH of 11 and 4.5. Batch biological treatment was conducted in shake flasks. Samples obtained during the treatments were monitored for BOD₅, COD, TOC, and molecular weight distribution. At an ozone dosage of 0.7-0.8 mg O₃/mL wastewater, integrated treatment showed about 30% higher TOC mineralization compared to individual ozonation or biotreatment. Ozone treatment enhanced the biodegradability of the effluent (monitored as 21% COD reduction and 13% BOD₅ enhancement), allowing for a higher removal of pollutants. The conversion of high molecular weight (HMW) to low molecular weight (LMW) compounds was an important factor in the overall biodegradability enhancement of the alkaline effluent. The overall biodegradability of the LMW compounds did not change over the course of ozonation, but it increased from 5% to 50% (measured as COD removal) for the HMW portion. Ozonation at pH of 11 was more effective than that at pH of 4.5 in terms of generating more biodegradable compounds.     

Occurrence and removal of pharmaceuticals and hormones through drinking water treatment

The occurrence of fifty-five pharmaceuticals, hormones and metabolites in raw waters used for drinking water production and their removal through a drinking water treatment were studied. Thirty-five out of fifty-five drugs were detected in the raw water at the facility intake with concentrations up to 1200 ng/L. The behavior of the compounds was studied at each step: prechlorination, coagulation, sand filtration, ozonation, granular activated carbon filtration and post-chlorination; showing that the complete treatment accounted for the complete removal of all the compounds detected in raw waters except for five of them. Phenytoin, atenolol and hydrochlorothiazide were the three pharmaceuticals most frequently found in finished waters at concentrations about 10 ng/L. Sotalol and carbamazepine epoxide were found in less than a half of the samples at lower concentrations, above 2 ng/L. However despite their persistence, the removals of these five pharmaceuticals were higher than 95%.     

Treatability of chloro-s-triazines by conventional drinking water treatment technologies

Recent research shows that herbicide atrazine (ATZ), simazine (SIM), and propazine (PROP), as well as their three chlorinated degrades-desethylatrazine (DEA), deisopropylatrazine (DIA), and didealkylatrazine (DDA)-may cause a common toxic effect in terms of endocrine disruption. The US Environmental Protection Agency (EPA) is currently considering a regulatory trigger based on the sum of these concentrations of these six chloro-s-triazines. While limited removal data exists for the parent compounds, little information is available for the degrades formed biologically and/or chemically in the environment and in the treatment plants. It is therefore critical to assess the removal efficiency in a typical water plant of the parent herbicides, as well as the daughter products. In this work, conventional drinking water treatment technologies were evaluated under typical water treatment plant conditions to determine their effectiveness in removing six chloro-s-triazines: ATZ, SIM, PROP, DEA, DIA, and DDA. Experiments were conducted using synthetic solutions prepared by spiking both distilled water and Missouri River water with the study compounds. Two powder activated carbons (PAC)--Calgon WPH and Norit HDB-were shown to be partially effective in removing the studied chloro-s-triazines. Ozonation efficiency varied, depending on different water sources, with respect to the removal of atrazine and didealkylatrazine. Coagulation/flocculation/sedimentation with alum and iron salts, excess lime/soda ash softening, and disinfection by free chlorine were all ineffective methods for removing chloro-s-triazines. It appears that chloro-s-triazine compounds are not readily removed by most conventional drinking water treatment processes, with the exception of use of activated carbon.     

Removal of bulk dissolved organic carbon (DOC) and trace organic compounds by bank filtration and artificial recharge

Bank filtration and artificial recharge provide an important drinking water source to the city of Berlin. Due to the practice of water recycling through a semi-closed urban water cycle, the introduction of effluent organic matter (EfOM) and persistent trace organic pollutants in the drinking water is of potential concern. In the work reported herein, the research objectives are to study the removal of bulk and trace organics at bank filtration and artificial recharge sites and to assess important factors of influence for the Berlin area. The monthly analytical program is comprised of dissolved organic carbon (DOC), UV absorbance (UVA254), liquid chromatography with organic carbon detection (LC-OCD), differentiated adsorbable organic halogens (AOX) and single organic compound analysis of a few model compounds. More than 1 year of monitoring was conducted on observation wells located along the flowpaths of the infiltrating water at two field sites that have different characteristics regarding redox conditions, travel time, and travel distance. Two transects are highlighted: one associated with a bank filtration site dominated by anoxic/anaerobic conditions with a travel time of up to 4-5 months, and another with an artificial recharge site dominated by aerobic conditions with a travel time of up to 50 days. It was found that redox conditions and travel time significantly influence the DOC degradation kinetics and the efficiency of AOX and trace compound removal.     

Simultaneous colour and DON removal from sewage treatment plant effluent: Alum coagulation of melanoidin

The aim of this study was to detect and characterise melanoidin in sewage treatment plant (STP) effluent, and to study the ability of alum coagulation to remove the colour and dissolved organic nitrogen (DON) associated with melanoidin. The melanoidin is non-biodegradable due to the complex cyclic based structure and thus it directly contributes to effluent nitrogen concentrations from the sewage treatment plant (STP). Lowering of effluent total nitrogen limits and the link between colour and chlorinated disinfection by-products have therefore driven a need to understand the structure, properties and treatability of DON species found in STP effluent.The focus of this paper is the refractory coloured, organic nitrogen compound melanoidin. Wetalla STP effluent has relatively high colour (170 mg-PtCo L⁻¹) and DON (2.5 mg L⁻¹) for a biological nutrient removal STP, owing to an industrial supply of melanoidin containing molasses fermentation wastewater. Alum coagulation jar tests were performed on synthetic melanoidin solution, STP effluent containing melanoidin (Wetalla, Toowoomba, Australia) and STP effluent free of melanoidin (Merrimac, Gold Coast, Australia) to examine the treatability of melanoidin and its associated colour and DON content when present in STP effluent.The removal of melanoidin from STP effluent resulted in significant colour and DON reduction. An alum dose of 30 mg L⁻¹ as aluminium was sufficient to reach maximum removal of colour (75%), DON (42%) and dissolved organic carbon (DOC) (30%) present in melanoidin containing STP effluent. Alum was shown to preferentially remove DON with a molecular weight >10 kDa over small molecular weight DON. Fluorescence excitation-emission matrix examination of the humic compounds present in the STP effluent indicated that melanoidin type humic compounds were more readily removed by alum coagulation than other humic compounds.     

Biodegradability of ozonation products as a function of COD and DOC elimination by example of substituted aromatic substances

Ozone pretreatment studies of nonbiodegradable substituted aromatic compounds were conducted to evaluate the effects of ozonation on the biodegradability of the oxidation products as a function of COD- DOC-elimination and ozone consumption.In the case of substituted aromatic compounds a 60–70% decrease of the COD-value and a 30–40% decrease of the DOC-value lead to biodegradable products (BOD₅-/COD = 0.4) independent of the pH and the initial concentration of compounds. To reach good biodegradability of the oxidation products 3 mg ozone on average per 1 mg initial DOC are necessary.     

Purification of cork processing wastewaters by ozone,by activated sludge,and by their two sequential applications

Wastewaters generated in the cork processing industry were treated in continuous reactors by means of single treatments separately-a chemical ozonation and an activated sludge system-and then by both sequential processes-ozonation followed by aerobic degradation, and aerobic degradation followed by ozonation. The removals obtained in the ozonation alone were 12-54%, 65-81%, and 55-89% for the COD, total phenolics, and absorbance at 254 nm, respectively, while the consumed ozone yield ranged from 40% to 61%, and the biodegradability (BOD(5)/COD) varied from an initial 0.60 to final values between 0.68 and 0.93. The optimum hydraulic retention time and ozone partial pressure were 3 h and 3 kPa, respectively. The stoichiometric ratio was 0.56 g of organic substrate degraded per g of ozone consumed, while the rate constants obtained for the ozone disappearance and for the organic matter degradation were 4490 L g COD(-1) h(-1) and 1970 L g O(3)(-1)h(-1) respectively. The presence of hydrogen peroxide or UV radiation in addition to ozone increased the values of organic matter removal as well as the stoichiometric ratio and the rate constants. The aerobic treatment by the activated sludge system yielded COD removals between 13% and 37% for hydraulic retention times between 24 and 96 h, and the Contois model gave values of q(max)=0.14 g COD g VSS(-1)h(-1) and K(1)=22.6 g COD g VSS(-1) for the main kinetic parameters. The sequential processes increased the substrate removal efficiencies in comparison with the individual processes. These enhancements were greater in the aerobic degradation-ozonation sequence than in the ozonation-aerobic degradation sequence.     

Ozonation and biological activated carbon filtration of wastewater treatment plant effluents

This study investigates the fate of trace organic chemicals (TrOCs) in three full-scale reclamation plants using ozonation followed by biological activated carbon (BAC) filtration to treat wastewater treatment plant effluents. Chemical analysis was used to quantify a wide range of TrOCs and combined with bioanalytical tools to assess non-specific toxicity (Microtox assay) and estrogenicity (E-SCREEN assay). Limited dissolved organic carbon (DOC) removal (<10%) was observed in the ozonation stages showing that oxidation leads to the formation of transformation products rather than mineralization. The quantified TrOCs were removed to a degree highly dependent on the compounds’ structures and the specific ozone dose (mg_O3 mg_DOC⁻¹). Non-specific toxicity was reduced by 31-39%, demonstrating that the mixture of remaining parent compounds and their transformation products as well as newly formed oxidation by-products had an overall lower toxic potential than the mixture of parent compounds. Estrogenicity was reduced by more than 87% indicating that the transformation products of the estrogenic chemicals lost their specific toxicity potential. The subsequent BAC filtration removed between 20 and 50% of the DOC depending on the plant configuration, likely due to biodegradation of organic matter. The filtration was also able to reduce the concentrations of most of the remaining TrOCs by up to 99%, and reduce non-specific toxicity by 33-54%. Overall, the combination of ozonation and BAC filtration can achieve removals of 50% for DOC and more than 90% for a wide range of TrOCs as well as a reduction of 70% of non-specific toxicity and more than 95% of estrogenicity. This process combination is therefore suggested as an effective barrier to reduce the discharge of TrOCs into the environment or their presence in water recycling schemes.     

Analysis of the mechanism of sludge ozonation by a combination of biological and chemical approaches

Using the practical sludge obtained from municipal sewage treatment plants, the mechanism of the sludge ozonation process was systematically investigated by a combination of biological and chemical approaches, including analysis of the changes in biological response by CFU and PCR-DGGE, bio-macromolecular activity and radical scavenging activity. The results indicated that after the sludge was exposed to ozone at less than 0.02 g O₃/g TSS, the DGGE fingerprint remained constant and there was still some enzyme activity, indicating that the sludge solubilization was the main process. At greater than 0.02 g O₃/g TSS, the bacteria began to be broken down and ozone was used to oxidize the bio-macromolecules such as proteins and DNA released from the sludge. Bacteria belonging to ‘G-Bacteria’ were able to conserve their DNA in the presence of less than 0.08 g O₃/g TSS. At levels higher than 0.10 g O₃/g TSS, the disintegration of the sludge matrix became slow and the microbes lost most of their activity, and ozone was used to transform the bio-macromolecules into small molecules. However, at levels higher than 0.14 g O₃/g TSS, the ozone failed to oxidize the sludge efficiently, because several radical scavengers such as lactic acid and SO₄²⁻ were released from the microbial cells in the sludge.     

Lincomycin solar photodegradation, algal toxicity and removal from wastewaters by means of ozonation

Antibiotic molecules have been reported among the xenobiotics present at trace levels in sewage treatment plant (STP) effluents and aquatic environment. Lincomycin, one of the most used in clinical practices whose presence in the STP effluents has been often documented, is submitted to an extensive investigation to assess its persistence in the environment and toxicity towards different algal strains. The possibility to remove the lincomycin from water by means of ozonation is demonstrated and a reduction of toxicity of ozonated solutions on S. leopoliensis, with respect to untreated solutions containing this compound, is obtained even just for 1h of treatment. Kinetic constants for the attack to lincomycin of ozone (from 1.53 x 10(5) M(-1)s(-1) at pH = 3.0 and 4.93 x 10(5) M(-1)s(-1) at pH = 6.7) and OH radicals (4.37 x 10(9) M(-1)s(-1) at pH = 5.5 and 4.59 x 10(9) M(-1)s(-1) at pH = 7.5) are also evaluated.