Removal of NOM in the different stages of the water treatment process

Natural organic matter (NOM) is abundant in natural waters in Finland and in many ways affects the unit operations in water purification. In this study, the organic matter content in water in different stages of a full-scale treatment process over 1 year was measured. The full-scale treatment sequence, studied at the Rusko water treatment plant in Tampere, Finland, consisted of coagulation, flocculation, clarification by sedimentation or flotation, activated carbon (AC) filtration, and disinfection. High-performance size exclusion chromatography (HPSEC) was used for separation to determine changes in the humic substances content during the purification process. In addition, total organic carbon (TOC), KMnO4-number, and UV-absorbance at wavelength 254 nm (UV254) were measured. High molecular weight (HMW) matter was clearly easier to remove in coagulation and clarification than low molecular weight (LMW) matter. Furthermore, depending on the regeneration of the activated carbon filters, activated carbon filtration was effective to a degree but did not remove most of the lowest molecular weight compounds. Significant correlation was established among HPSEC, KMnO4, UV254 absorbance, and TOC. HPSEC proved to be a fast and relatively easy method to estimate NOM content in water and, in fact, gave more information than traditional methods on the type of NOM in a water sample. It also helped the process performance follow-up.     

Basic characterization of Norwegian NOM samples — Similarities and differences

NOM (natural organic matter) samples, isolated by reverse osmosis (RO), and nine NOM samples, concentrated by low-pressure, low-temperature evaporation (EVA) from various origin in Norway, were characterized by different methods. The methods included elemental content of the freeze-dried samples (C, H, N, and O), elemental content of the redissolved samples (DOC, Na, Ca, Cu, Fe, and Mn), specific spectral absorbance at λ = 254 nm (A(254 nm)/DOC) and at λ = 436 nm (A(436 nm)/DOC), UV/Vis-spectra, specific fluorescence (excitation and emission spectra), proton capacity, Cu-complexation capacity, and content of hydrolysable amino acids and carbohydrates. In addition, chromatographic characterization by gel chromatography and reversed-phase chromatography was done. Studies on adsorption and flocculation abilities and the formation of trihalomethanes (THM) and organic halogens adsorbable on activated carbon (AOX) upon chlorination were also investigated. Comparison of the results showed that the samples were different according to the origin of the sample, isolation procedure, and time of sampling. The differences are not the same for all parameters used. Standardized procedures have to be applied to redissolve the organic material in water in order to compare data. For the samples investigated, it was shown that parameters like elemental analysis (H/C ratio), the specific spectral absorption in the UV range, proton capacity, complexation capacity and anionic particle charge, amount of hydrolysable amino acids and carbohydrates, adsorption behaviour on activated carbon, and the THM-FP are sensitive parameters to show differences concerning origin and isolation procedure.     

Monitoring natural organic matter in water with scanning spectrophotometer

This study uses scanning ultraviolet-visible (UV-Vis) spectrophotometer to monitor natural organic matter (NOM) in water. The results showed that the area under the UV-Vis spectra is a good surrogate to monitor the concentration of the aqueous NOM. No apparent difference was found between the spectra of the three commercially available humic acids used in this study. The use of the scanning spectra compensates the potential random error in the absorbance determined at single wavelength due to the heterogeneous NOM compositions. The major interference of the proposed method comes from the formazine turbidity and nitrate nitrogen (NO3- -N). Although filtration with a 0.45-microm filter can remove most of the interference from formazine, some interference is still present at a wavelength less than 250 nm. Also it is found that the presence of the NO3- -N greatly affect the spectra of the NOM. In order to monitor the NOM in water with minimized interference, it is recommended that the area under the spectra between 250 and 350 nm should be used as a surrogate for concentration of NOM in water.     

Isolation of natural organic matter — The influence on the assimilable organic carbon

The biofilm formation potential (BFP), determined by the assimilable organic carbon (AOC), was measured in water samples containing natural organic matter (NOM), and in “identical” samples reconstructed from NOM isolated by reverse osmosis (RO) and dissolved in distilled water. The results showed identical BFP in natural and reconstructed NOM water samples within the standard deviation of the AOC measurements. These results indicate that the composition of the NOM is the single most important parameter for the BFP of natural waters, and that the RO isolation of NOM produces a powder which, after dissolution in distilled water, is representative for the natural water containing NOM with regard to BFP determined by AOC.     

Characterization of natural organic matter by pyrolysis/GC-MS

Natural organic matter (NOM) in nine water samples selected for the NOM typing project were characterized by pyrolysis in conjunction with gas chromatography and mass spectrometry (GC-MS). NOM samples both isolated by reverse osmosis and evaporation techniques were subjected to high temperature pyrolysis and the products obtained were assigned to one of the four main types: biopolymers carbohydrates, proteinaceous materials, N-acetylamino sugars, and polyhydroxy aromatics. These biopolymers in the water samples were quantified and the quantities were used in characterization. Principal component analysis was employed in revealing the similarities and differences between the samples and between the separation techniques. The results indicate that there are little differences between the samples, and the NOM separated by evaporation preserves most of the organic material compared to the reverse osmosis technique.     

Characterization of natural organic matter from eight Norwegian surface waters: The effect of ash on molecular size distributions and CHN content

Natural organic matter (NOM) was isolated by reverse osmosis (RO) from eight surface waters in southern Norway. The freeze-dried samples were reconstituted in deionized water and part of the sample was dialysed against HCl. Samples of both the dialysed and non-dialysed materials were then ultrafiltered to give fractions: >50 000 dal., <50 000 but >10 000 dal. and <10 000 dal. nominal molecular weights (NMW). Dialysis against acid reduced the ash content of the samples by 68±14%. Non-dialysed NOM has a preponderance of carbon in the largest fraction (52.7±30%), while after dialysis, the smallest fraction of NOM has the greatest carbon content (52.2±9.7%). In addition to altering the overall apparent size distributions of the NOM fractions, dialysis generally reduces the amount of nitrogen relative to carbon in the NOM samples. The latter observation appears to be the result of losses of small molecular size organic matter that is enriched in nitrogen.     

Characterization of natural organic matter from eight Norwegian surface waters: Proton and copper binding

As a part of the International NOM-Typing Project, proton and copper binding studies were conducted on ultrafiltered (>1000 dal.) and dialysed (>100 dal.) natural organic matter (NOM) samples from eight Norwegian Lakes. The NOM samples were similar with respect to proton and copper binding, although minor differences were observed among the samples of different origin. Slight variations occurred for seasonal changes and lime additions. The proton binding pK_a values grouped in three distinct classes: pK_a1 = 4.20–4.28; pK_a2 = 6.61–6.87; and pK_a3 = 9.27–9.8. The average total proton binding site concentration of the NOM samples was: 12.7 meq/g total organic carbon (TOC). Two binding sites were established for copper with average log K1 = 4.84 and log K2 = 7.17. The average site concentration for samples isolated by reverse osmosis (RO) was 0.56 μmol/mg C. Copper binding characteristics appear to be influenced by the method of sample isolation. For NOM isolated by low pressure evaporation (evap), binding site concentrations are smaller, conditional stability constants are higher, variability of the copper complexation capacity is smaller, and correlation with elemental composition (C, N, H) is better than in the case of NOM isolated by RO.     

Capillary zone electrophoretic studies on Norwegian surface water natural organic matter

Capillary zone electrophoresis (CZE) is a useful tool for the analysis of the electrophoretic behavior of anionic polyelectrolytes like humic substances. CZE was used to compare natural organic matter (NOM) with high ash content obtained by reverse osmosis (RO) and low temperature, low pressure evaporation (Ev.) from different Norwegian surface water sources. The quantitative relation between the resulting electrophoretic signals (peak height and area) and the carbon amount of the injected NOM samples was found linear. The NOM gave homogeneous signals in CZE, with a distribution of the detection signals around an average electrophoretic mobility (AEM) corresponding to the charge density distribution of the NOM, governed by the distribution of their molecular sizes and acidities. Like humic substances, NOM only appears as anions in capillary electrophoresis (CE), but the high ash content of these samples and the presence of metals strongly influenced their mobilities at lower pH. CZE could be used as a tool for the rapid evaluation of the average net charge and the molecular radius of the NOM at pH 5.1.     

Changes of AhR-mediated activity of humic substances after irradiation

Humic substances (HS) and natural organic matter (NOM) are natural organic compounds ubiquitous in the environment. However, some studies indicate that both HS and NOM can act as xenobiotics, e.g. induce hormone-like effects in fish, amphibians and invertebrates. Molecules of these substances contain a number of aromatic rings and conjugated double bonds--the so called chromophores. Irradiation of dissolved HS and NOM can lead to a series of photochemical reactions which can act on these substances itself, or on other substances present in aquatic environment along with HS and NOM such as e.g. xenobiotics. In our previous study, we have found significant interactions of five humic acids (HA) with cytosolic aryl hydrocarbon receptor (AhR) in an in vitro bioassay based on H4IIE-luc cells. In the present study, we have studied the changes in AhR-mediated activities both of HS and NOM after irradiation that simulated natural solar light. Nine different HS and two NOM samples were irradiated in Pyrex tubes with a medium-pressure mercury lamp for a duration of 0 to 52 h (which corresponds to 0-52 d natural solar radiation). Original concentrations of the samples were 50 mg L(-1), and the greatest concentration of HS and NOM photoproducts subsequently tested in the bioassay was 17 mg L(-1), which is an environmentally relevant concentration. After irradiation the absorbances of all the samples were less than the original materials. The AhR-mediated activity of the HA-Fluka and HA Sodium Salt were partially decreased by irradiation. The activities of other HS and NOM, that were either AhR-active or -inactive were not changed by irradiation. The results of the study demonstrate that AhR-mediated activities of two active HA is caused by both photo-stable and photo-labile AhR activators, while the other three active HA contain only photo-stable AhR activators. Potential mechanisms of the observed irradiation-induced changes in AhR-mediated activities are discussed.     

Natural organic matter in drinking water — The “NOM-typing project”, background and basic characteristics of original water samples and NOM isolates

The complex nature of natural organic matter (NOM), and the impact of this matter on drinking water quality, necessitate international co-operative efforts. After several decades of struggle, many experienced NOM scientists world wide recognize the need for international sample references, or better yet, to work together on the same set of samples. The aim of the “NOM-typing project” was a multi-method characterization of a limited number of NOM samples, isolated from different water sources. The background of the project and the nature of the sampling sites are described here, and some data comparing the composition of the samples, before and after the isolation, are presented. The techniques used for isolation were reverse osmosis (RO) and evaporation (EVA). The NOM samples were isolated from eight different locations in the southern part of Norway. The nature of the corresponding catchments differs, however, all samples were from areas with no influence of agriculture or local industry. The key issue of the project was that all samples were isolated with exactly the same methods and by the same team. In spite of the uniformity of the isolation technique used for the nine samples, the recoveries of the material differ from sample to sample. Generally, the loss of NOM is in the range of 10%, however, for one sample, the loss was as high as 35%. These discrepancies are probably partly because of differences in the nature of the NOM and partly due to differences in the general composition of the ambient water. There are a few remarkable differences between the nine samples. There was a high percentage of ash in isolates from acidified areas. These are also the samples where the loss of NOM during the isolation process was highest. The density of the RO-isolates differs 10-fold between the samples. The lipophilisity of the NOM samples, expressed as relative solubility in octanol, differs more than 30-fold.     

Multi-site proton interactions with natural organic matter

Water samples from various locations in Norway were used to isolate natural organic matter (NOM). The NOM was isolated using both reverse osmosis and low-pressure low-temperature evaporation for each sample site. These samples were titrated from −log[H⁺] 3 to 11 at 0.1 unit intervals. The data were analyzed using the Discrete Site Analysis (DISI) technique for pK_a intervals of 0.2. The acidity constants are grouped into four classes: strong (pK_a < 5), intermediate strong (5.1 < pK_a < 7.5), intermediate weak (7.6 < pK_a < 9.2), and weak (pK_a > 9.3). All samples, regardless of isolation method, were found to contain strong and weak ligands, along with some intermediate ligands. For the same sample site, the concentration of these ligands were found to be dependent on isolation method and titration direction (acid then base vs. base then acid). In addition, the concentration and classes of ligands present were found to vary between sample sites. Suwannee River fulvic acid was analyzed as a reference sample, and was qualitatively similar to the NOM samples but quantitatively different. Overall, the differences in pKa spectra due to isolation method and/or titration direction are almost as significant as differences between sample location, but there are no consistent trends in effects of isolation method or titration direction on characterization of NOM.     

Pre-assessment of the speciation of 60Co, 125Sb, 137Cs and 241Am in a contaminated aquifer

A sample of contaminated groundwater was analyzed using a combination of wet techniques to obtain geochemical information on the mobile species of 60Co, 125Sb, 137Cs and 241Am. The techniques were combined in a scheme to determine the predominant character of the radionuclides in negative or positive fractions, size separation by ultrafiltration, and their association with natural organic matter (NOM). The analyses indicated that the radionuclides of interest were predominantly in the negative fraction. Most of the 60Co and 125Sb were in the small size fraction (<5000 Da), and 137Cs and 241Am were found with the larger, colloidal-sized material. Antimony-125 and 60Co were predominantly in the hydrophilic fraction, while 137Cs and 241Am were found in hydrophobic fractions. Our analysis indicated that 137Cs is found in the same fraction as the large-sized colloidal (hydrophobic) material, suggesting an association with NOM. The results suggested that 60Co and 241Am were associated with NOM, in different size fractions, suggesting that these two nuclides are bound to different sites. Finally, the 125Sb results were inconclusive, whether this nuclide is associated with NOM, or it is inorganic.     

Transport of NOM and trace metals through macropores in the Lake Skjervatjern catchment

In the dystrophic Lake Skjervatjern, located at the west coast of Norway, periods with high precipitation coincide with an increase in the concentrations of natural organic matter (NOM) and several trace elements. The lake has no visual inlets, and, during high flow periods, a major part of the drainage follows macropores, entering the lake 10–40 cm below the surface. Water from the lake and the macropores were fractionated according to size by means of a hollow fiber ultra-filtration technique, during two periods with high precipitation. In the macropores, the high molecular weight form of NOM (nominal molecular cut off > 10 kDa) appears to be an important transporting agent for several trace elements that strongly interact with NOM (e.g., Fe, Al, Pb, Sm, La, Ce, and Eu). In contrast, anionic (V and As) and acid sensitive (Mn and Cs) elements were, generally, at a low molecular weight form (nominal molecular cut off < 3 kDa). The latter showed similar or lower concentrations in the macropores compared to the lake water, and NOM were apparently of small importance as a carrier for V, As, Mn, and Cs. Differences in concentration and size distribution of trace elements between the macropores and the lake basins indicate that parts of NOM and associated trace elements that enter the lake in a high molecular weight form, undergo aggregation and gravitational settling and thereby become a part of the lake sediments.     

Fluorescence analysis for multi-site aluminum binding to natural organic matter

Natural organic matter (NOM) samples isolated from different water sources in Norway were compared using their fluorescence properties. Fluorescence surfaces were observed at pH 4.36 and deconvoluted using SIMPLISMA (Windig and Guilment 1991). There were a total of seven different fluorophores observed for these samples and each sampling site had between four and six of the fluorescent components. These components were observed to bind Al during titrations at the same pH. Multiresponse titration curves were fit using the method of Smith and Kramer (1998) and most of the binding strengths are similar to values for Suwannee River fulvic acid (logK' between 4.8 and 5.5), but there are strong sites (logK' = 7) and weak sites (logK' between 3 and 4) also observed. Results depended on the isolation method used; reverse osmosis and low pressure evaporation yielded different values but with no consistent trends.     

Efficiency of the activated carbon filtration in the natural organic matter removal

The removal and transformation of natural organic matter were monitored in the different stages of the drinking water treatment train. Several methods to measure the quantity and quality of organic matter were used. The full-scale treatment sequence consisted of coagulation, flocculation, clarification by flotation, disinfection with chlorine dioxide, activated carbon filtration and post-chlorination. High-performance size-exclusion chromatography separation was used to determine the changes in the humic substances content during the purification process; in addition, a UV absorbance at wavelength 254 nm and total organic carbon amount were measured. A special aim was to study the performance and the capacity of the activated carbon filtration in the natural organic matter removal. Four of the activated carbon filters were monitored over the period of 1 year. Depending on the regeneration of the activated carbon filters, filtration was effective to a degree but did not significantly remove the smallest molar mass organic matter fraction. Activated carbon filtration was most effective in the removal of intermediate molar mass compounds (range 1,000-4,000 g/mol). Regeneration of the carbon improved the removal capacity considerably, but efficiency was returned to a normal level after few months.     

Changes in physicochemical forms of lead and cadmium added to freshwater

Transformation of physicochemical forms of cadmium and lead added at 1 μ/L to Lake Michigan water have been studied by anodic stripping voltammetry. Unfiltered, 0.45 μ membrane filtered, ultrafiltered, and UV irradiated ultrafiltered samples were used to differentiate metal binding by particulate, colloidal, and dissolved organic matter. The reaction of added metal with colloids and particles is rapid. Their reaction with soluble organic matter is slow, requiring 1 to 2 days for complexation of one-half the added metal.     

Influence of alumina coating on characteristics and effects of SiO2 nanoparticles in algal growth inhibition assays at various pH and organic matter contents

Silica nanoparticles (NPs) belong to the industrially most important NP types. In a previous study it was shown that amorphous SiO(2) NPs of 12.5 and 27.0 nm are stable in algal growth inhibition assays and that their ecotoxic effects are related to NP surface area. Here, it was hypothesized and demonstrated that an alumina coating completely alters the particle-particle, particle-test medium and particle-algae interactions of SiO(2) NPs. Therefore, stability and surface characteristics, dissolution, nutrient adsorption and effects on algal growth rate of both alumina coated SiO(2) NPs and bare SiO(2) NPs in OECD algal test medium as a function of pH (6.0-8.6) and natural organic matter (NOM) contents (0-12 mg C/l) were investigated. Alumina coated SiO(2) NPs aggregated in all media and adsorbed phosphate depending on pH and NOM concentration. On the other hand, no aggregation or nutrient adsorption was observed for the bare SiO(2) NPs. Due to their positive surface charge, alumina coated SiO(2) NPs agglomerated with Pseudokirchneriella subcapitata. Consequently, algal cell density measurements based on cell counts were unreliable and hence fluorescent detection of extracted chlorophyll was the preferred method. Alumina coated SiO(2) NPs showed lower toxicity than bare SiO(2) NPs at concentrations ≥46 mg/l, except at pH 6.0. At low concentrations, no clear pH effect was observed for alumina coated SiO(2) NPs, while at higher concentrations phosphate deficiency could have contributed to the higher toxicity of those particles at pH 6.0-6.8 compared to higher pH values. Bare SiO(2) NPs were not toxic at pH 6.0 up to 220 mg/l. Addition of NOM decreased toxicity of both particles. For SiO(2) NPs the 48 h 20% effect concentration of 21.8 mg/l increased 2.6-21 fold and a linear relationship was observed between NOM concentration and effective concentrations. No effect was observed for alumina coated SiO(2) NPs in presence of NOM up to 1000 mg/l. All experiments point out that the alumina coating completely altered NP interactions. Due to the difference in surface composition the SiO(2) NPs, which had the smallest surface area, were more toxic to the alga than the alumina coated SiO(2) NPs. Hence, surface modification can dominate the effect of surface area on toxicity.     

长期有机物循环对红壤稻田养分及水稻生长的影响

通过长期有机物循环的定位试验,研究了长期有机物循环利用对红壤稻田养分供应及水稻生长发育的影响,目的是了解长期有机物循环利用后土壤养分含量变化、水稻生长特性及两者的相关性。结果表明有机物循环明显提高了土壤有机质含量,并使土壤养分维持在一个相对较高的水平上。有机物循环处理的土壤有机质,全N、全P和全K及其有效部分的平均含量分别比无循环处理提高了445％、347％、175％、94％,特别是碱解N,速效P和速效K含量提高显著,有机物循环处理比无循环处理提高达469％、452％和347％。有机物循环利用提高了水稻分蘖数和叶面积指数,使水稻群体的透光率减少。有机物循环处理平均单叶净光合速率比无循环处理高68％,蒸腾作用比无循环处理高50％,最终表现为干物质积累量及稻谷产量的增加。对长期有机物循环利用后的红壤稻田养分指标与水稻生长指标进行逐步回归分析后发现,土壤中速效P及有机质含量的增加是促进水稻生长的主要因素.     

Effects of natural and chemical stressors on Enchytraeus albidus: Can oxidative stress parameters be used as fast screening tools for the assessment of different stress impacts in soils?

Enchytraeids are important organisms of the soil biocenosis. They improve the soil pore structure and the degradation of organic matter. These organisms are used in standardized testing, using survival and reproduction (6 weeks) as endpoints. The use of biomarkers, linked to ecologically relevant alterations at higher levels of biological organization, is a promising tool for Environmental Risk Assessment. Here, enchytraeids were exposed for different time periods (two days and three weeks) to different soils (OECD artificial soil, different compositions in its organic matter, clay or pH value, and LUFA 2.2 natural soil) and different chemicals (Phenmedipham and copper). The main question addressed in the present study was if the effects of chemicals and different soil properties are preceded by alterations at the sub-cellular level, and if these endpoints may be used reliantly as faster screening tools for the assessment of different stress conditions in soils. The parameters measured in E. albidus whole body were: lipid peroxidation (LPO), total glutathione (TG), as well as the enzymatic activities of superoxide dismutase (SOD), catalase (CAT), glutathione reductase (GR), glutathione peroxidase (GPx) and glutathione S-transferase (GST). The results showed that biomarker responses in E. albidus were significantly affected by the soil type (GST, CAT, GPx, GR and LPO) and the duration of exposure in OECD artificial soil (GST, GPx, GR, CAT and LPO) but not in LUFA 2.2 natural soil. For the abiotic factors studied, after 2 days, low pH decreased significantly the TG levels and the activities of CAT and GR,and low OM also significantly decreased CAT and GR activities. After 3 weeks, differences in soil properties caused a decrease in GR and GPx activities, whereas increased GST activity was observed due to low organic matter and pH. Copper significantly increased the activities of CAT, GPx and GR, and decreased the activity of GST after 2 days as well as inscreasing LPO levels after 3 weeks. Phenmedipham increased LPO levels, associated with increased levels of TG as well as increased activities of CAT and GPx and decreased GST activity after 3 weeks exposure. This study shows that both abiotic and chemical stresses could be followed through biomarker analysis and that some of these determinations are potential endpoints in a quick soil contamination assessment procedure.     

Acid-base characteristics of organic carbon in the HUMEX lake Skjervatjern

The Humic Lake Acidification Experiment (HUMEX) was launched in 1988 to study the role of humic substances in the acidification of surface waters and the impacts of acidic deposition on the chemical and biological properties of humic substances. This subproject was designed to determine the contribution of organic acids to the acidity of Lake Skjervatjern (the HUMEX Lake) and the impacts of the acidification on the characteristics of organic carbon. In order to get an empirical measure for organic acidity, dissolved organic carbon (DOC) was fractionated, isolated, and base-titrated from each half of Lake Skjervatjern. Hydrophobic acids were the dominant organic carbon fraction; the total organic acid content was generally greater than 80% of the DOC. The reliability of the fractionation procedure was tested with synthetic acids and the Nordic Fulvic acid. The DOC fractions did not show high variation over the 1.5-y acidification period. Hydrophilic acids had consistently greater exchange acidities compared to hydrophobic acids, averaging 12.9 μeq/mg DOC vs. 10.9 μeq/mg DOC, respectively. The dissociation of organic acids during acid-base titrations clearly increased with increasing pH. The high organic anion contribution to the ion balances indicates that humic matter is an important acidity source in Lake Skjervatjern. There are slight signs that the contribution of organic acids to overall lake acidity has decreased since acidification was initiated.