The fate and importance of organics in drinking water treatment: a review

In the pioneer days, the main driving forces for research of organics in drinking water treatment (DWT) were human health risks and optimisation of technology. The focus was on natural organic matter (NOM) structure, disinfection by-products (DBPs) formation, NOM removal by means of coagulation, adsorption, and oxidation, and development of the most efficient water treatment trains. Surprisingly, after decades of research, rapid development of analytical techniques and progress in risk assessment, the same driving forces are still in the limelight — although the topics have changed slightly. The attention switched from trihalomethanes to a new generation of DBPs. The definition of hydrophilic/hydrophobic NOM depends on the technique used for characterisation. It has become evident that numerous organic compounds can threaten water supply sources. Some of them had been ignored or overlooked in the past, but have recently been detected by advanced analytical tools even in drinking water. Prioritisation becomes priority per se. As far as processes are concerned, mainstream research has been following three lines: fouling mechanisms, application of hybrid processes and interactions between synthetic organic chemicals, other water constituents and materials used in DWT. Significant development has been made in membrane technology. This paper presents a broad overview of the recent organics research. Although the state-of-the-art technologies seem to have an answer to each and every question raised, it is still necessary to deal with specific problems on a case-by-case basis mainly due to the unique nature of NOM and different xenobiotics that may appear in various types of waters. In the end, human health risk, which derives from the presence/absence of organics, is only the tip of the iceberg — underneath lies a whole new universe — the socio-economic aspect of water treatment and quality that deserves much more attention.     

The impact of seasonal variations in DOC arising from a moorland peat catchment on coagulation with iron and aluminium salts

Natural organic matter (NOM) is one of the main sources of environmental pollution to drinking water supplies in much of the UK and the US. Whilst traditional treatment with trivalent coagulants has proven a successful strategy in the past, operational problems are now being reported during periods of elevated organic levels in the water. Characterisation of the pollutants in terms of polarity, molecular weight and charge, provides a method to understand the impact of the observed temporal and spatial variations in terms of a mechanistic parameter relevant to the treatment processes. Results from this study demonstrate that it is not simply the increased organic concentration, but also the change in NOM composition and character, which influences the impact on the treatment processes. Consequently, monitoring of these parameters provides an insight into how to manage the impact caused by environmental changes to the catchments.     

四种净水工艺对水源水微量有机物去除的研究

以UV254和CODMn代表饮用水源水中有机物替代指标.对常规处理、生物陶粒预处理、生物滤池、生物活性炭(BAC)、颗粒活性炭(GAC)、纳滤和光催化氧化进行组合,形成不同的处理流程,研究各流程对UV254和CODMn的去除效果.结果表明,各工艺流程都有一定的处理效率,其中以生物滤池和纳滤为主的组合流程处理效果最佳.此流程对UV254的去除率接近100%,CODMn的去除率达到78.6%,大大提高了饮用水的安全性.     

Molecular size distribution of natural organic matter in raw and drinking waters.

The purpose of this study was to compare the molecular size distribution (MSD) of natural organic matter (NOM) in raw waters (RW) and drinking waters (DW), and to find out the differences between MSD after different water treatment processes. The MSD of NOM of 34 RW and DW of Finnish waterworks were determined with high-performance size-exclusion chromatography (HPSEC). Six distinct fractions were generally separated from water samples with the TSK G3000SW column, using sodium acetate at pH 7 as an eluent. Large and intermediate humic fractions were the most dominant fractions in surface waters (lakes and rivers), while in artificially recharged groundwaters and natural groundwaters intermediate and small fractions predominated. Water treatment processes removed the two largest fractions almost completely shifting the MSD towards smaller molecular size in DW. Granular activated carbon (GAC) filtration, ozonation, and their combination reduced all humic fractions compared to the conventional treatment. Humic fractions correlated with total organic carbon (TOC) content and chemical oxygen demand, this being especially true in RW. The results demonstrate that the HPSEC method can be applied for a qualitative and also for rough estimate quantitative analyzes of NOM directly from RW and DW samples without sample pretreatment.     

Use of an ultraviolet light-activated persulfate process to degrade humic substances: effects of wavelength and persulfate dose

Environmental Science and Pollution Research - Natural organic matter (NOM), commonly found in surface and ground waters, form disinfection by-products in drinking water. Generally, advanced...     

Changes in the nature of dissolved organics during pulp and paper mill wastewater treatment: a multivariate statistical study combining data from three analytical techniques

The paper-making process can produce large amounts of wastewater (WW) with high particulate and dissolved organic loads. Generally, in developed countries, stringent international regulations for environmental protection require pulp and paper mill WW to be treated to reduce the organic load prior to discharge into the receiving environment. This can be achieved by primary and secondary treatments involving both chemical and biological processes. These processes result in complex changes in the nature of the organic material, as some components are mineralised and others are transformed. In this study, changes in the nature of organics through different stages of secondary treatment of pulp and paper mill WW were followed using three advanced characterisation techniques: solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy, pyrolysis-gas chromatography mass spectrometry (py-GCMS) and high-performance size-exclusion chromatography (HPSEC). Each technique provided a different perspective on the changes that occurred. To compare the different chemical perspectives in terms of the degree of similarity/difference between samples, we employed non-metric multidimensional scaling. Results indicate that NMR and HPSEC provided strongly correlated perspectives, with 86 % of the discrimination between the organic samples common to both techniques. Conversely, py-GCMS was found to provide a unique, and thus complementary, perspective.     

Removal of pollutants from surface water and groundwater by nanofiltration: overview of possible applications in the drinking water industry

During the last decade, nanofiltration (NF) made a breakthrough in drinking water production for the removal of pollutants. The combination of new standards for drinking water quality and the steady improvement of the nanofiltration process have led to new insights, possible applications and new projects on lab-scale, pilot scale and industrial scale. This paper offers an overview of the applications in the drinking water industry that have already been realised or that are suggested on the basis of lab-scale research. Applications can be found in the treatment of surface water as well as groundwater. The possibility of using NF for the removal of hardness, natural organic material (NOM), micropollutants such as pesticides and VOCs, viruses and bacteria, salinity, nitrates, and arsenic will be discussed. Some of these applications have proven to be reliable and can be considered as known techniques; other applications are still studied on laboratory scale. Modelling is difficult due to effects of fouling and interaction between different components. The current insight in the separation mechanisms will be briefly discussed.     

Effect of copper(II) on natural organic matter removal during drinking water coagulation using aluminum-based coagulants.

Coagulation has been proposed as a best available technology for controlling natural organic matter (NOM) during drinking water treatment. The presence of heavy metals such as copper(II) in source water, which may form copper-NOM complexes and/or interact with a coagulant, may pose a potential challenge on the coagulation of NOM. In this work, the effect of copper(II) on NOM removal by coagulation using alum or PAX-18 (a commercial polymerized aluminum chloride from Kemiron Inc., Bartow, Florida) was examined. The results show that the presence of 1 to 10 mg/L of copper(H) in the simulated waters improved the total organic carbon (TOC) removal by up to 25% for alum coagulation and by up to 22% for PAX-18 coagulation. The increased NOM removal with the presence of copper(II) in the waters can most likely be ascribed to the formation copper-NOM complexes that may be more adsorbable on aluminum precipitates and to the formation of copper(II) co-precipitates that may also adsorb NOM. The presence of 1 to 5 mg/L of copper(I) in the waters containing 3 mg/L NOM as carbon was reduced below the maximum contaminant level goal (1.3 mg/L as copper) using either coagulant. The results suggest that the presence of copper(H) in source water may not adversely affect the NOM removal by coagulation. A good linear correlation was observed between the TOC removal efficiency and the log-total moles of the precipitated metals, which include the metal ion from a coagulant and the divalent metal ion(s) in source water.     

Natural organic matter (NOM) in roof runoff and its impact on the Fe0 treatment system of dissolved metals

The present work investigates the impacts and mechanisms associated with natural organic matter (NOM) in the Fe0 treatment system of Cu2+ and Zn2+ under roof runoff conditions. The NOM in runoff waters was characterized using XAD-4/8 adsorption resins, copper complexation, acidic capacity and liquid chromatography with online carbon detection. Batch kinetic experiments and flow-through configurations were performed and the results of metal removal were elucidated taking into account the characteristics of NOM. Based on the findings, it is shown that NOM influences the removal of metals through several complex pathways. At an un-favored condition for adsorption of metals, i.e., on iron corrosion products, at pH相似文献   

Synthesis and characterisation of Pd-modified N-doped TiO2 for photocatalytic degradation of natural organic matter (NOM) fractions

Introduction

The removal of natural organic matter (NOM) from water is becoming increasingly important in order to prevent the formation of carcinogenic disinfection by-products. The inadequate removal of NOM has a bearing on the capacity of the other treatment processes to remove organic micro-pollutants or inorganic species that may be present in the water. New methods are therefore currently being sought to effectively characterise NOM and also to ensure that it is sufficiently removed from drinking water sources.

Methodology

Nitrogen- and palladium-co-doped TiO₂ was synthesised by a modified sol?Cgel method and evaluated for its photocatalytic degradation activity on NOM fractions under simulated solar radiation. The photocatalyst was characterised by FT-IR, Raman, XRD, DRUV?Cvis, SEM, TEM, EDS, XPS and TGA. FT-IR confirmed the presence of OH groups on thermally stable, nearly spherical anatase nanoparticles with an average diameter of 20?nm. PdO species appeared on the surface of the TiO₂ as small uniformly dispersed particles (2 to 3?nm). A red shift in the absorption edge compared to commercial anatase TiO₂ was confirmed by DRUV?Cvis. In order to gain a better insight into the response of NOM to photodegradation, the NOM was divided into three different fractions based on its chemical nature.

Results and discussion

Photodegradation efficiencies of 96, 38 and 15?% were realised for the hydrophobic, hydrophilic and transphilic NOM fractions, respectively. A reasonable mechanism was proposed to explain the photocatalytic degradation of the NOM fractions. The high photocatalytic activity could be attributed to the larger surface area, smaller crystalline size and synergistic effects of the co-dopants N and Pd in the TiO₂ crystal.     

A new approach to data evaluation in the non-target screening of organic trace substances in water analysis

Non-target screening via high performance liquid chromatography-mass spectrometry (HPLC-MS) has gained increasingly in importance for monitoring organic trace substances in water resources targeted for the production of drinking water. In this article a new approach for evaluating the data from non-target HPLC-MS screening in water is introduced and its advantages are demonstrated using the supply of drinking water as an example. The crucial difference between this and other approaches is the comparison of samples based on compounds (features) determined by their full scan data. In so doing, we take advantage of the temporal, spatial, or process-based relationships among the samples by applying the set operators, UNION, INTERSECT, and COMPLEMENT to the features of each sample. This approach regards all compounds, detectable by the used analytical method. That is the fundamental meaning of non-target screening, which includes all analytical information from the applied technique for further data evaluation. In the given example, in just one step, all detected features (1729) of a landfill leachate sample could be examined for their relevant influences on water purification respectively drinking water. This study shows that 1721 out of 1729 features were not relevant for the water purification. Only eight features could be determined in the untreated water and three of them were found in the final drinking water after ozonation. In so doing, it was possible to identify 1-adamantylamine as contamination of the landfill in the drinking water at a concentration in the range of 20 ng L⁻¹. To support the identification of relevant compounds and their transformation products, the DAIOS database (Database-Assisted Identification of Organic Substances) was used. This database concept includes some functions such as product ion search to increase the efficiency of the database query after the screening. To identify related transformation products the database function “transformation tree” was used.     

Application of semipermeable membrane device for assessing toxicity in drinking water

Semipermeable membrane devices (SPMDs) mimic passive diffusive transport of bioavailable hydrophobic organic compounds through biological membranes and their partitioning between lipids and environmental levels. Our study was developed on a surface water treatment plant based in Turin, Northern Italy. The investigated plant treats Po River surface water and it supplies about 20% of the drinking water required by Turin city (about one million inhabitants). Surface water (input) and drinking water (output) were monitored with SPMDs from October 2001 to January 2004, over a period of 30 days. The contaminant residues, monthly extracted from SPMDs by dialysis in organic solvent, were tested with the Microtox^TM acute toxic test and with the Ames mutagenicity test. Same extracts were also analyzed with gaschromatography—mass spectrometry technique in order to characterise the organic pollutants sampled, especially Polycyclic Aromatic Hydrocarbons (PAHs).

Although the PAHs mean concentration is about one hundred times lower in the output samples, the mean toxic units are similar in drinking and surface water.

Our data indicate that the SPMD is a suitable tool to assess the possible toxicity in drinking water.     

Formation of hazardous by-products resulting from the irradiation of natural organic matter: comparison between UV and VUV irradiation

The use of ultraviolet (UV) or vacuum ultraviolet (VUV) photo-oxidation followed by biological treatment for the removal of natural organic matter (NOM) in drinking water is a potential water treatment technique under investigation. This paper reports on the trihalomethane formation potential (THMFP), the haloacetic acid formation potential (HAAFP), and formation of nitrite and peroxide following both UV and VUV irradiation of NOM prior to biological treatment. The total THMFP was found to decrease with increasing UV and VUV irradiation dose, although there was a linear increase in bromoform formation. Determination of the THMFP of NOM fractions obtained after irradiation, showed that the hydrophobic fraction was dominated by chlorinated species which accounted for the majority of the total THMFP, while bromoform was observed only in the hydrophilic fraction of NOM. VUV irradiation reduced the HAAFP with increasing dose, in contrast, UV irradiation had a limited effect on the overall HAAFP. Following UV or VUV irradiation, the chlorinated species accounted for the majority of HAAFP; however, significant formation of brominated haloacetic acid (HAA) was observed. The nitrate concentration of the untreated water directly influenced the concentration of nitrite produced as a consequence of UV and VUV irradiation. Hydrogen peroxide formation was greater during VUV irradiation than during UV irradiation. Samples exposed to various doses of UV or VUV irradiation (up to 138 J cm(-2)) were deemed non-cytotoxic (African green monkey kidney cells) and non-mutagenic (Ames test).     

Adsorption of natural organic matter from waters by iron coated pumice

Natural pumice particles were used as granular support media and coated with iron oxides to investigate their adsorptive natural organic matter (NOM) removal from waters. The impacts of natural pumice source, particle size fraction, pumice dose, pumice surface chemistry and specific surface area, and NOM source on the ultimate extent and rate of NOM removal were studied. All adsorption isotherm experiments were conducted employing the variable-dose completely mixed batch reactor bottle-point method. Iron oxide coating overwhelmed the surface electrical properties of the underlying pumice particles. Surface areas as high as 20.6m(2)g(-1) were achieved after iron coating of pumice samples, which are above than those of iron coated sand samples reported in the literature. For all particle size fractions, iron coating of natural pumices significantly increased their NOM uptakes both on an adsorbent mass- and surface area-basis. The smallest size fractions (<63 microm) of coated pumices generally exhibited the highest NOM uptakes. A strong linear correlation between the iron contents of coated pumices and their Freundlich affinity parameters (K(F)) indicated that the enhanced NOM uptake is due to iron oxides bound on pumice surfaces. Iron oxide coated pumice surfaces preferentially removed high UV-absorbing fractions of NOM, with UV absorbance reductions up to 90%. Control experiments indicated that iron oxide species bound on pumice surfaces are stable, and potential iron release to the solution is not a concern at pH values of typical natural waters. Based on high NOM adsorption capacities, iron oxide coated pumice may be a promising novel adsorbent in removing NOM from waters. Furthermore, due to preferential removal of high UV-absorbing NOM fractions, iron oxide coated pumice may also be effective in controlling the formation of disinfection by-products in drinking water treatment.     

Enhancement effect of water associated with natural organic matter (NOM) on organic compound-NOM interactions: a case study with carbamazepine

Natural organic matter (NOM) in soils and sediments is recognized to strongly affect environmental distributions of organic compounds. Water associated with NOM may have a significant impact on NOM-organic compound interactions. The objectives of this research were (1) to determine the effect of hydration of a model NOM sorbent on interactions with a probe organic compound, carbamazepine (CBZ), and (2) based on the comparison with the literature data, to evaluate the effect of organic compound structure on the cooperative participation of water molecules in organic sorbate-NOM interactions. CBZ is one of the most widely reported water pollutants from the pharmaceutical and personal care products family. Therefore, CBZ sorption on Pahokee peat was compared from water and from n-hexadecane, using solubility-normalized solute concentrations. CBZ-NOM interactions were enhanced by one to two orders of magnitudes when NOM became fully hydrated. This enhancement is associated with the distinct ability of CBZ to undergo strong, specific interactions with NOM which was revealed by comparing the transfer of CBZ and another model sorbate, phenanthrene, from solution in n-hexadecane to the hydrated NOM sorbent. The enhancing effect of NOM hydration on CBZ-NOM interactions was also observed when CBZ sorption was examined on partially hydrated NOM. In comparison with a smaller-size organic sorbate such as phenol, CBZ needs more NOM-associated water in order to demonstrate the strengthening of interactions with NOM. Therefore, for penetration of the larger sorbate molecules into the NOM interior, a greater number of water molecules are needed to compensate for the local NOM disintegration thus suggesting the greater extent of the cooperativity in an involvement of water molecules in the CBZ-NOM interactions.     

Influence of pH and ozone dose on the content and structure of haloacetic acid precursors in groundwater

This study investigated the effects of pH (6-10) and ozone dose [0.4-3.0?mg O(3)/mg dissolved organic carbon (DOC)] on the content and structure of haloacetic acid (HAA) precursors in groundwater rich in natural organic matter (NOM; DOC 9.85?±?0.18?mg/L) during drinking water treatment. The raw water was ozonated in a 2 L glass column. NOM fractionation was carried out using XAD resins. HAA formation potential (HAAFP) was determined according to standard EPA Method 552. NOM characterization revealed it is mostly hydrophobic (65?% fulvic and 14?% humic acids). Hydrophobic NOM significantly influences HAA formation, as confirmed by the high HAAFP (309?±?15?μg/L). Ozonation at pH?6-10 led to changes in NOM structure, i.e. complete humic acid oxidation, and increased the hydrophilic NOM fraction content (65-90?% achieved using 3.0?mg O(3)/mg DOC). The highest degree of NOM oxidation and HAA precursor removal was achieved at pH?10 (up to 68?% HAAFP). Ozonation pH influenced the distribution of HAA precursor content, as increasing the pH from 6 to 10 increased the reactivity of the hydrophilic fraction, with the HAAFP increasing from 19.1?±?6.0?μg/mg DOC in raw water to 152?±?8?μg/mg DOC in ozonated water. The degree of HAA precursor removal depends on the dominant oxidation mechanism, which is related to the applied ozone dose and the pH of the oxidation process. Ozonation at pH?10 favours the mechanism of radical NOM oxidation and was the most effective for HAAFP reduction, with the efficacy of the process improving with increasing ozone dose.     

Separation of finely dispersed sorbents from purified water by ultra-flocculation and turbulent micro-flotation

This paper describes studies of the process of recovery of finely dispersed sorbents from water by means of ultra-flocculation, sedimentation and turbulent micro-flotation, and the sequential combination of these steps. With reference to the most commonly used finely dispersed sorbents in the purification of water from organic contaminants, heavy metals and radio nuclides (aluminium hydroxide, sodium montmorillonite and nickel ferrocyanide), it has been shown that this approach is at least four times more effective for industrial wastewater purification and treatment of drinking water.     

Powdered activated carbon coupled with enhanced coagulation for natural organic matter removal and disinfection by-product control: application in a Western Australian water treatment plant

The removal of organic precursors of disinfection by-products (DBPs), i.e. natural organic matter (NOM), prior to disinfection and distribution is considered as the most effective approach to minimise the formation of DBPs. This study investigated the impact of the addition of powdered activated carbon (PAC) to an enhanced coagulation treatment process at an existing water treatment plant on the efficiency of NOM removal, the disinfection behaviour of the treated water, and the water quality in the distribution system. This is the first comprehensive assessment of the efficacy of plant-scale application of PAC combined with enhanced coagulation on an Australian source water. As a result of the PAC addition, the removal of NOM improved by 70%, which led to a significant reduction (80-95%) in the formation of DBPs. The water quality in the distribution system also improved, indicated by lower concentrations of DBPs in the distribution system and better maintenance of disinfectant residual at the extremities of the distribution system. The efficacy of the PAC treatment for NOM removal was shown to be a function of the characteristics of the NOM and the quality of the source water, as well as the PAC dose. PAC treatment did not have the capacity to remove bromide ion, resulting in the formation of more brominated DBPs. Since brominated DBPs have been found to be more toxic than their chlorinated analogues, their preferential formation upon PAC addition must be considered, especially in source waters containing high concentrations of bromide.     

Effect of lipids on sorption/desorption hysteresis in natural organic matter

The chemical composition and physical conformation of natural organic matter (NOM) play a major role in regulating its capacity to retain hydrophobic organic compounds. Naphthalene and phenanthrene were used to study the correlations between sorption/desorption isotherm nonlinearity and compositional data obtained from quantitative ¹³C solid-state DPMAS NMR spectroscopy for soil and peat organic matter with or without lipids. Sorption experiments were conducted using a batch equilibration method. Desorption experiments were carried out immediately following the sorption experiments by three successive decant-refill cycles. Hysteresis was observed in all samples. Nonlinear sorption behavior was increased by removal of lipids from the NOM. The hysteresis index, obtained from the ratio of the Freundlich exponents (N values) for the desorption and sorption isotherms, was lower in the lipid-extracted NOM samples than in the same samples without lipid extraction. The relationship between the extent of hysteresis and the characteristics of the ¹³C DPMAS NMR spectra indicates that altering NOM composition through lipid extraction not only increased the proportion of aromatic-C content, but also increased sorption/desorption hysteresis. Our data also suggest that the hysteresis index is negatively related to aromaticity.     

壳聚糖对地表水中污染物的净化作用

综述了壳聚糖絮凝剂对地表水中悬浮物、天然有机物(NOM)、人工合成有机物(SOCs)、藻类的去除和对细菌的抑制及残留铝的削减作用。壳聚糖在地表水净化中具有一定的应用价值。