Elimination of Swimming Pool Water Disinfection By‐products with Advanced Oxidation Processes (AOPs)

Ozonation is a treatment step which was first applied in the 1960s in pool water treatment for disinfection as well as for oxidation of pool water contaminants. Contact time between ozone and pool water was identified to be of significance with an increased elimination efficiency regarding chloramines, trihalogenmethane formation potential and the permanganate index for longer reaction times. Oxidation via OH radicals might be the dominating pathway. In this study ozonation was compared with the ozone based advanced oxidation processes ozone/UV and ozone/hydrogen peroxide regarding the elimination efficiency of both disinfection by‐products (DBPs) and DBP precursors. It was observed that AOPs in comparison to ozonation showed an increased elimination efficiency regarding total organic carbon (TOC), the organically bound halogens adsorbable on activated carbon (AOX) and AOX formation potential. A contact time of 3 minutes between pool water and oxidant turned out to be practically sufficient. Just for the trihalomethane (THM) formation potential ozonation showed a slight advantage compared to the AOPs because ozonation is a highly selective oxidant and OH radical reactions are known to produce small reactive molecules which are easier transformed to THMs. Combination of membrane filtration and AOPs resulted in an elimination of 10 to 90 % of the DBPs and their precursors. The ozone/hydrogen peroxide process is suggested for pool water treatment because of the higher elimination rates compared to ozonation and of economic reasons compared to the ozone/UV process.     

Influence of Oxidative Treatment on the AOX‐formation Potential of Aromatic Sulfonates

Aromatic sulfonates can be found in drinking water. Thus, they must have passed water treatment and survived ozonation. Degradation of aromatic sulfonates can be achieved by the UV/H2O2‐process. Since drinking water is often treated with chlorine as a disinfectant, the formation of disinfection by‐products has to be considered. Therefore, the production of AOX (on activated carbon adsorbable organic halogens) after chlorination of the sulfonates with and without preoxidation was investigated. Instead of the analysis of the individual degradation products, the determination of the sum parameter AOX was used as a fast screening method. The investigated sulfonates were: anthraquinone‐2‐sulfonate, naphthalene‐2‐sulfonate, 2‐aminonaphthalene‐1‐sulfonate, and 4,4′‐diaminostilbene‐2,2′‐disulfonate. All sulfonates containing amino groups showed high potentials of AOX formation. The preoxidation with ozone increased the potentials of AOX formation in general. Treating the sulfonates by using the UV/H2O2‐process, the formation potentials run to zero after going through a maximum value.     

Bildung bromhaltiger Desinfektionsnebenprodukte nach Chlorung von Bodenseewasser in Abhängigkeit von Aufbereitungsschritten und der Bromidkonzentration

Formation of Brominated Disinfection By-products after Chlorination of Water from Lake Constance Depending on Treatment Steps and Bromide Concentration The formation of halogenated disinfection by-products (DNP) (trihalomethanes (THM), haloacetic acids (HES), haloacetonitriles (HAN), haloketones (HKE) and chloropicrin (TCNM)) was studied after chlorination (0.5 mg/L) of raw water and drinking water from Lake Constance. The objectives of this study were to investigate the effect of bromide ion on the distribution of DNP-species resulting from chlorination and to draw up a bromide mass-balance. The treatment of water from Lake Constance with ozone decreased the formation of DNP about 35% and of total organic halogens (AOX) about 45%. This decline in DNP-formation is mainly due to the formation of chloroform, dichloro- and trichloroacetic acid. Though there is only a small amount of bromide (6.2 μg/L) in water from Lake Constance, about 32% of THM, 16% of HES, and 30% of HAN contained bromine after chlorination of treated water. The addition of bromide ion (up to 1 mg/L) shifted the DNP-composition to more brominated species. The distribution of the DNP-species depends on the initial molar bromide-to-chlorine ratio. A mathematic model showed the same pattern of DNP-species depending on the initial molar bromide-to-chlorine ratio that was observed experimentally in microstrained raw water and drinking water from Lake Constance. After chlorination of microstrained raw water, 27% of the bromide were incorporated in known DNP, 34% in unknown substances, and about 39% of bromide were not converted to organic bromine. After chlorination of treated water, only 16% of the bromide were incorporated in unknown substances, whereas 34% were found in known DNP. About 50% were found as bromide again. After addition of bromide (up to 25 μg/L) to ozonated and treated water from Lake Constance, between 60 and 72% of the bromide that had reacted after chlorination were found in analyzed low-molecular DNP.     

Characterization of AOX by Fractionation Analysis and Size‐exclusion Chromatography

A characterization method for AOX in surface water samples was developed and tested. The method involves fractionation using a hydrophobic C18 resin and a weak anionic exchange resin and allows the fractionation of the AOX pool of surface water samples into four fractions: (1) hydrophilic acidic, (2) hydrophilic non‐acidic, (3) hydrophobic acidic, and (4) hydrophobic non‐acidic. The adsorption analysis was verified with AOX‐relevant model compounds and was applied to characterize the AOX pool of a stream sample from the Moskva river (Russia). In addition to the fractionation analysis, size‐exclusion chromatography was used to characterize the AOX pool of the sample studied. Hydrophilic acids made up the major fraction of the AOX pool (55 %). Among this fraction chlorinated high‐molecular acids (humic substances) made up the main fraction (35 %).     

AOX‐Bildung bei der sonolytischen Oxidation von Salicylsäure in Gegenwart von Chlorid

AOX‐formation by the Sonochemical Treatment of Salicylic Acid in Presence of Chloride Ultrasound shows great potential for improving water, wastewater and sludge treatment processes. However, a number of questions exist: for example the influence of suspended solids or salts. In this paper the influence of chloride in view of AOX‐formation should be investigated. As organic model compound salicylic acid (0.05…1 mmol/L) was used. Formation of AOX (adsorbable organically bound halogens) was measured in dependence upon chloride concentrations (1.4…141 mmol/L) and pH 2 and 9. Ultrasound irradiation was performed in glass reactor (500 mL) at 206 kHz and 353 kHz by continuous bubbling argon:oxgen (4:1) at a flow rate of 1 L/min into the solutions. The elimination of salicylic acid and the formation of hydrogen peroxide were not influenced by the presence of chloride (up to 56 mmol/L). The rate of salicylic acid elimination and the formation rate of hydrogen peroxide are at concentrations of mmol/(L min) levels but those of AOX formation of μmol/(L min) levels. The reactions leading to chlorinated by‐products can be seen as minor reaction paths. The yield of AOX depending on frequency, pH and chloride concentration lies between 10 μg/L and 900 μg/L. In acidic medium they were twice as high as in basic medium. Below the ratio chloride : salicylic acid of 2 mol/mol, AOX could not be identified.     

Zur Bildung von Artefakten und deren Vermeidung bei der Bestimmung leichtflüchtiger Halogenkohlenwasserstoffe in Wasser mittels Headspace-Gaschromatographie unter den Bedingungen der DIN 38407 Teil 5 (DEV-F5). Teil II: Überhöhte Trihalogenmethanbefunde in gechlortem Schwimmbeckenwasser

Formation of Artefacts and its Suppression during the Determination of Volatile Halogenated Hydrocarbons in Water by Means of Headspace Gas Chromatography under the Standard Conditions of DIN 38407-F5. Part II: Increased Trihalomethane Formation in Chlorinated Swimming-pool Water A comparison of two analytical standard procedures for the determination of trihalomethanes (THM) in water (headspace gas chromatography and pentane extraction/gas chromatography) yielded strongly differing results. Under the conditions recommended by the German Standard Method DIN 38407-F5 (60…80°C for at least 60 min) degradation of thermo-labile chlorination products occurs resulting in elevated THM concentrations. The reactions involved are partly pH-dependant, and these can be suppressed by sample acidification. The degradation of trihalogen acetic acids, however, can only be influenced by minimizing the equilibration time and temperature. Other intermediate chlorination products (haloacetonitriles) are also degraded to THM after preceding hydrolysis to the corresponding carboxylic acids. Comparative results obtained with a purge and trap method at ambient temperature, i.e. without thermal stress during the enrichtment step, are lower than with static headspace GC but still high in comparison to the pentane extraction method. Presumably volatile THM-precursors are also trapped and subsequently decomposed upon thermal desorption from the trap. As the static headspace GC is the most rational method of LHKW determination available, the recommended experimental sample handling conditions should be modified in a way that deterioration reactions are reduced as far as possible.     

Organic Halogen Group Parameters as Indicators of Ground Water Contamination

A regional survey of Danish ground water demonstrated the presence of adsorbable organic halogens (AOX) in almost all of 142 wells (99 percent). Generally, the presence of AOX was not related to point or non-point source contamination with halogenated organics. However, the AOX concentrations varied with the geology of the aquifers. Extractable organic halogens (EOX) and volatile organic halogens (VOX) were far less prevalent (detected in 4 percent of sampled wells) and the detection could, in most cases, be explained by contamination or chlorination of the wells. The VOX concentrations corresponded to the concentrations of identified, volatile contaminants. The study demonstrates the presence of a natural background level of AOX in the investigated aquifers. This must be considered in the interpretation of AOX results as an indicator of ground water contamination with haloorganics. Similar background levels of EOX or VOX were not delected.     

Einflußfaktoren auf die Freisetzung von DOC und AOX unter ehemaligen Abwasserversickerungsflächen

Factors Influencing the Release of DOC and AOX out of Former Wastewater Infiltration Soils The influence of soil and of infiltration water quality on the release of dissolved organic carbon (DOC) and adsorbable organic halogens (AOX) from two former wastewater infiltration sites was investigated in laboratory column studies. Desorption was the most important factor influencing release processes. It depends on the amount of sorbent and sorbate and the strength of binding. Therefore, for constant irrigation rates a higher soil organic carbon content coincided with higher DOC-contents of the column effluent, while the irrigation water quality was of minor importance. Within one system the dependencies of AOX release and DOC mobilization were found to be similar. Transferring these dependencies on other systems has its limitations because of a different binding quality between sorbent and sorbate.     

The removal of dissolved humic acids and iron during estuarine mixing

The estuarine chemistry of dissolved humic acids was determined by carrying out both field and laboratory studies. These approaches were combined in an investigation of the Amazon estuary while laboratory mixing experiments were performed using filtered (0.45?0.001 μm) river water fractions of the Water of Luce (Scotland).The results demonstrate that a small fraction of river dissolved organic matter is preferentially and rapidly flocculated during estuarine mixing. This fraction is the high molecular weight component of dissolved humic acids (0.45?0.1 μm filtered). Approximately 60–80% of the dissolved humic acid in these rivers flocculates during estuarine mixing. This represents a removal of only 3–6% of river dissolved organic matter and is responsible for the non-conservative behaviour of dissolved humic acid in the Amazon estuary even though total dissolved organic carbon appears conservative.The salinity dependence with which humic acid flocculates in estuaries is similar to that of iron. This implies that both constituents may be removed from river water by a common mechanism of colloid flocculation.     

Potentially Bioavailable Natural Organic Carbon and Hydrolyzable Amino Acids in Aquifer Sediments

This study evaluated the relationship between concentrations of operationally defined potentially bioavailable organic ‐carbon (PBOC) and hydrolyzable amino acids (HAAs) in sediments collected from a diverse range of chloroethene‐‐contaminated sites. Concentrations of PBOC and HAA were measured using aquifer sediment samples collected at six selected study sites. Average concentrations of total HAA and PBOC ranged from 1.96 ± 1.53 to 20.1 ± 25.6 mg/kg and 4.72 ± 0.72 to 443 ± 65.4 mg/kg, respectively. Results demonstrated a statistically significant positive relationship between concentrations of PBOC and total HAA present in the aquifer sediment (p < 0.05). Higher levels of HAA were consistently observed at sites with greater levels of PBOC and first‐order decay rates. Because amino acids are known to be readily biodegradable carbon compounds, this relationship suggests that the sequential chemical extraction procedure used to measure PBOC is a useful indicator of bioavailable carbon in aquifer sediments. This, in turn, is consistent with the interpretation that PBOC measurements can be used for estimating the amount of natural organic carbon available for driving the reductive dechlorination of chloroethenes in groundwater systems.     

Continuous fluorescence assessment of organic matter variability on the Bournbrook River,Birmingham, UK

Continuous monitoring of dissolved organic matter (DOM) character and concentration at hourly resolution is rare, despite the importance of analysing organic matter variability at high‐temporal resolution to evaluate river carbon budgeting, river water health by detecting episodic pollution and to determine short‐term variations in chemical and ecological function. The authors report a 2‐week experiment performed on DOM sampled from Bournbrook, Birmingham, UK, an urban river for which spectrophotometric (fluorescence, absorbance), physiochemical (dissolved organic carbon [DOC], electrical conductivity, pH) and isotopic (D/H) parameters have been measured at hourly frequency. Our results show that the river had sub‐daily variations in both organic matter concentration and characteristics. In particular, after relatively high‐magnitude precipitation events, organic carbon concentration increased, with an associated increase in intensity of both humic‐like and tryptophan‐like fluorescence. D/H isotopic ratio demonstrates different hydrological responses to different rainfall events, and organic matter character reflects this difference. Events with precipitation < 2 mm typically yielded isotopically heavy water with relatively hydrophilic DOM and relatively low specific absorbance. Events with precipitation > 2 mm had isotopically lighter water with higher specific absorbance and a decrease in the proportion of microbially derived to humic‐like fluorescence. In our heavily urbanized catchment, we interpret these signals as one where riverine DOM is dominated by storm sewer‐derived ‘old’ organic matter at low‐rainfall amounts and a mixed signal at high‐precipitation amounts where ‘event’ surface runoff‐derived organic matter dominate during storm sewer and combined sewer overflow routed DOM. Copyright © 2009 John Wiley & Sons, Ltd.     

Using Chlorine Dioxide to Remove the Fouling of Ultrafiltration Membrane and Control Disinfection By‐Products

Ultrafiltration (UF) can remove natural organic matter (NOM) effectively. Moreover, chlorine dioxide (ClO₂) has been an alternative disinfectant as it forms fewer disinfection by‐products with NOM than chlorination does. Therefore, combining ClO₂ with UF may improve conventional purification processes. In this study, feed water containing humic acid with 4.07 mg/L total organic carbon (TOC) was dosed directly with various amounts of ClO₂ (0, 2, 5, 10, and 15 mg/L) before being filtered through a 5‐kDa UF membrane. With a low dose (2 mg/L ClO₂), UF removed humic acid effectively, as TOC was not detected in the permeate, and the permeate flux increased to about 80% of the initial permeate flux by cross flow. Moreover, the concentrations of ClO, ClO, and trihalomethanes in the permeate were below the United States Environmental Protection Agency guidelines.     

Human‐induced sedimentation patterns of a channelized lowland river

Channelization of the severely polluted Odra and Vistula Rivers in Poland induced intensive accumulation of fine‐grained deposits rich in organic matter and heavy metals. These sediments have been identified in vertical profiles in a narrow zone along river banks both in groyne‐created basins and on the floodplain. Grain size, organic matter, zinc (Zn), lead (Pb), copper (Cu) content and cesium‐137 (¹³⁷Cs) was used for sediment dating and, stratigraphy and chemistry have been diagnostic features for these deposits, named industrial alluvium. In the most polluted river reaches stabilized by bank reinforcements and groynes, 2‐m‐thick slack water groyne deposits are composed of uniform strata of polluted silts with organic matter content over 10%, Zn content over 1000 mg/kg and average Cu and Pb over 100 mg/kg. The average rate of sediment accretion in groynes is higher than on the floodplain and reaches 5 cm/yr. Stratification which appears at higher levels in the groyne fields and on the levees reflects a change from in‐channel to overbank deposition and is typified by dark layers separated by bright, sandy, and less polluted strata. Stratified, 4‐m‐thick, sediment sequences have been found in groyne fields of incised river reaches. The average rate of sediment accretion in these reaches is of the order of 5 cm/yr. In stable and relatively less polluted river reaches, vertical‐accretion organic deposits are finely laminated and the average rate of deposition amounts to a few millimeters per year. Investigations indicate that groyne construction favors conditions for long‐term storage of sediments at channel banks. For this reason, groynes should be considered as structures that efficiently limit sudden release of sediment‐associated heavy metals stored in channels and in floodplains of the historically polluted rivers. Copyright © 2014 John Wiley & Sons, Ltd.     

Chloride and Organic Chlorine in Soil

Chloride is ubiquitous in soil, but the past years of research have revealed that organic matter also contains chlorine, in amounts similar to that of phosphorus. Hence, one of the major constituents of soil organic matter has previously been overlooked, and still very little is known about the turnover of organic chlorine in soil. In spite of the obvious connection between chloride and organic chlorine, organic chlorine rarely is considered when the biogeochemical cycling of chloride is in focus, and chloride rarely is taken into account when the occurrence and formation of natural organic chlorine compounds are in focus. The aim of the paper is to review ten years of research concerning the biogeochemical cycling of organic chlorine in soil, and to tie the biogeochemical cycling of organic chlorine to that of chloride.     

Alkaline Degradation of Dissolved Organic Matter

The degradation of dissolved organic matter (DOM) was studied in alkaline solution. The products were characterised using UV/vis spectroscopy, size‐exclusion chromatography (SEC), and by the analysis of low‐molecular‐weight organic acids (LMWOA). The degradation experiments were performed with water from a brown water lake or its isolated fulvic acid fraction and sodium hydroxide at different reaction times and temperatures. Depending on the wavelength and the reaction time, the UV/vis absorbance between 230 nm and 600 nm increased or decreased. The behaviour of model compounds during reactions in alkaline media was compared to the UV/vis spectroscopic behaviour of DOM. The release of LMWOA was described by kinetic data and compared to the data of model reactions. Evidence was given for the carboxylic esters playing a significant role in the release of LMWOA only during the beginning of the alkaline degradation. The results gained by SEC with on‐line UV and DOC detection showed that the average size of DOM was decreasing, and that a major part of the degradation products consisted of low‐molecular‐weight mono‐ and dicarboxylic acids.     

Investigations on the Biodegradability of Chlorinated Fulvic Acids Untersuchungen zur mikrobiellen Verwertbarkeit gechlorter Fulvinsäuren

Microbial biodegradation of organic substances takes place during drinking water treatment, but also in the distribution net, if the drinking water still contains biodegradable organic substances. This phenomenon is called regrowth. The regrowth potential of a drinking water is high, when for instance ozonation is used as the last step of treatment. It was proved before, that ozonation increases the biodegradability of humic substances, which are the main fraction of organic carbon in drinking water. In this work the objective was to check, if chlorination has a similar effect on humic substances. Using the method developed by Werner of measuring the regrowth potential of a water it could be shown by dilution series with chlorinated and unchlorinated humic substances that the substrate quality of these organics is increased by chlorination. The better substrate quality is seen in the chlorinated solutions, which might contain also low molecular weight organic compounds, but also in the fulvic acid fraction after XAD-enrichment, which removes most of the low molecular weight organic compounds. The chlorination creates in the fulvic acid solutions a shift of molecular size to smaller molecules and higher polar substances, which might be the reasons for the better biodegradability. From these results it can be concluded, that chlorination produces substances, which are more easily biodegradable. But this will not produce regrowth problems as long as there is free chlorine present as a disinfectant. In contrast, when the chlorine demand is very high and no free chlorine is left, this might produce high colony counts in the distribution net.     

Environmental effect of produced water from North Sea oil operations

Produced water from North Sea oil reservoirs contains substantial amounts (about 1g I⁻¹) of non-hydrocarbon organic matter, largely as salts of acetic, propionic and butyric acids, as well as some 20–40 mg I⁻¹ of dissolved hydrocarbons such as benzene, toluene and xylene. The non-hydrocarbon components originate in water in the oil-bearing formation. All of the organic matter can be accounted for, within analytical accuracy. The water also contains some 20–30 mg I⁻¹ of ammoniacal nitrogen and a number of inorganic components.At peak water production from production installations in the North Sea some 1−2 × 10⁵ tonnes yr⁻¹ of organic acids will be discharged in the U.K. sector of the North Sea.The ready biodegradability of the organic constituents and the low toxicity of produced water have been confirmed by direct measurement; acute toxicity is unlikely at dilutions of greater than 100 fold.Dispersion has been modelled and tested in the laboratory indicating some 1000 fold dilution within less than 50 m of the discharge.The laboratory studies are supported by field observations. Any direct deleterious effects are limited to the immediate vicinity of the discharge (within a few tens of metres).     

Electrochemical Ozone Production as an Environmentally Friendly Technology for Water Treatment

Perspectives, advances and environmental aspects concerning electrochemical ozone production applied to water purification are presented and discussed in relation to the conventional corona process (silent electric discharge). Ozone generated using a laboratory‐made electrochemical reactor was applied for the discoloration/degradation of dyes used in the Brazilian textile industry and for degradation of endocrine disruptors. A constant ozone load of 0.35 ± 0.02 g/h was used throughout. The study, concerning color removal from dye solutions, revealed that total discoloration is rapidly achieved. The degradation rate of the textile dyes evaluated by TOC is little affected by the dye composition and considerably influenced by the pH and ozonation time. Analysis of the COD/TOC‐ratio indicates that ozonation increases oxidation feasibility of the organic matter (dye by‐products) when compared to the original compounds. Ozonation of mixed aqueous solutions containing different endocrine disruptors revealed these compounds are totally degraded with a very high removal rate.     

On the use of UV spectrophotometry to assess dissolved organic carbon origin variations in the Upper Rhône River

To detect temporal changes and the origin of the refractory dissolved organic matter in the Upper Rhône River, UV light absorbance (A) at 285 nm and quantitative dissolved organic carbon (DOC) measurements were carried out. Data from 63 visits to the main channel over a period of two years and from visits to different waterbodies in the alluvial plain before and after a flood are presented. There was a good correlation between A (0.019–0.160) and the DOC content (1.40–9.81 mg/L) for the waterbodies, but not for the river axis with lower A (0.013–0.044) and DOC content (1.13–2.20 mg/L). Due to this good correlation, the DOC content could be quantified for the waterbodies by absorbance measurements only. For the river water this indirect determination of the DOC content was not possible. However, the A/DOC ratio showed changes in the composition of DOC of river water and provided indications about the origin of the dissolved organic matter in the Upper Rhône River.     

Die Desinfektion von Trinkwasser — ein kritischer Überblick

In the chlorination of drinking water about 90% of chlorine show an oxidizing effect, 10% result in halogenated reaction products, ca. 1% of them consisting of trihalomethanes. When chlorine dioxide is applied, in most the trihalomethanes remain below the detection limit, but increasingly polar organic reaction products originate, on the other hand. Chloramine is rarely applied, mostly for securing transport with storage reservoir waters. Only little information about reaction products is available. By the application of ozone one obtains a wide spectrum of reaction products, the aldehyde contents can be influenced by activated carbon. Especially critical is the formation of persistent epoxides, above all from pesticides. Due to antimon burners, the ultraviolet irradiation is gaining in interest, and in many cases its biocidal effect is superior to that produced by chlorination and ozonization, except for the problem of re-germination in the water supply network. The costs of ultraviolet irradiation, however, are much higher than those of the other techniques, of which chlorination causes only about one quarter of the costs of the other chemical disinfection techniques.