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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Biological vs. chemical properties of natural organic matter isolated from selected Norwegian lakes

Relationships among different spectroscopic, chemical, and biological properties of dissolved natural organic matter (NOM) were investigated. NOM samples were isolated by means of reverse osmosis from eight Norwegian lakes. Elemental composition, absorption spectra (UV, VIS, IR), the influence on algal growth, and accumulation rates of metals by mussels in the presence of NOM were measured. Linear regression and principal components analyses were utilised to assess relationships between the biological and chemical properties. It was concluded that the content of organic matter in the isolates and the aromaticity of NOM, as characterised by UV and VIS spectra, are best correlated with the biological properties.     

崇明东滩盐沼表层沉积物有机碳空间分布特征及其来源示踪研究

沉积物有机碳空间分布特征及其来源是盐沼碳循环研究的一个关键问题。该研究分析了长江口崇明东滩盐沼表层沉积物样品总有机碳(TOC)、总氮(TN)和稳定碳同位素(δ13C)等参数。研究表明:东滩表层沉积物TOC和TN的平均值分别为7. 70±3. 74和0. 74±0. 32 g/kg,两者均表现为自北向南减少的分布趋势。沉积物δ13C平均值为-25. 05±1. 21‰,三元混合模型模拟计算结果表明东滩沉积物有机碳主要来源于悬浮颗粒物(43. 53±22. 44%)和植被(43. 29±24. 82%),底栖微藻贡献率较低(13. 20±8. 40%)。东滩北部沉积物表现为高悬沙贡献-低植被贡献-高有机碳含量特征,中南部表现高植被贡献-低悬沙贡献-低有机碳含量的特点。     

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.     

Characterisation of NOM by adsorption parameters and effective diffusivities

Adsorption equilibria were studied with RO isolates for both activated carbon and activated alumina. Maximum carbon loadings on the order of 65 mg/g DOC were obtained, while the maximum loadings of activated alumina were about 30 mg/g DOC. In the latter case the slope of the isotherms was generally steeper, indicating weaker adsorbabilities of some of the NOM compounds on the metal oxide adsorbent. Since NOM must be regarded as a multi-component system with respect to adsorption, the data were evaluated by the adsorption analysis procedure. The results were used for a theoretical comparison of NOM adsorption based on the same initial concentration of all samples. The method of colloidal titration was applied to the RO isolates in the range pH = 3–8. Poly-DADMAC was used as a cationic polymer, and a streaming current instrument was used for end point detection. The results which are termed anionic colloidal charge (ACC) values increase with increasing pH for pH = 3–6 while they are about constant for pH = 6–8. At the samples' original pH, the specific ACC values found range from 5.2 to 7.6 meq/g DOC. Mass transfer coefficients for NOM adsorption on granular activated carbon were determined for both RO and EVAP isolates, respectively. The data were used to derive effective diffusivities for each sample. The results differ by a factor of about 2 with the Maridalsvann sample having the highest and the Humex sample having the lowest diffusivity. Furthermore, the results for the EVAP isolates are in 8 of 9 cases higher than for the RO samples. Based on a comparison with known macromolecules, average molecular weight values were estimated to be on the order of 700–4800 Dalton.     

保护性耕作下蚕豆生育期土壤有机碳、氮含量变化与分布特征

为研究西南紫色土丘陵区坡耕地长期保护性耕作下旱作蚕豆不同生育时期农田土壤有机碳、氮相关组分分布特征,进而优化保护性耕作措施、改善土壤肥力。试验采用传统耕作、垄作、传统耕作+秸秆半量覆盖、垄作+秸秆半量覆盖、传统耕作+秸秆全量覆盖、垄作+秸秆全量覆盖6个处理。结果表明:在不同处理下,土壤总有机碳(TOC)、总氮(TN)、活性有机碳(AOC)、颗粒有机碳(POC)、水溶性氮(DN)的含量分布均表现出0～1010～20 cm土层,且随时间变化整体波动均不大。蚕豆生育期内,无秸秆覆盖条件下,垄作较平作提高了土壤总有机碳、土壤全氮、活性有机碳和颗粒有机碳的含量,但在秸秆覆盖条件下,垄作却降低了土壤总有机碳和颗粒有机碳的含量,且随着秸秆覆盖量的增加土壤颗粒有机碳和活性有机碳含量下降。同时,无论平作或垄作,秸秆覆盖较无秸秆覆盖均有利于土壤总有机碳、土壤全氮、活性有机碳和颗粒有机碳含量的提升。相关性分析表明,TOC与TN、DN、AOC之间呈显著正相关,TN与POC、DN、AOC之间呈显著正相关,POC仅表现出与DOC显著正相关,DOC与DN呈极显著正相关,DN则与AOC为极显著正相关关系。总之,单一垄作措施或秸秆覆盖能更有利于改善土壤碳、氮状况,且土壤有机碳、氮不同组分之间存在一定的耦合关系。     

Removal of hydrocarbons from Nile water

The need to remove hydrocarbons from water supply sources raises questions on the efficiency of the present water treatment processes in removing hydrocarbons. Therefore, the effectiveness of physicochemical processes involving chlorination, chemical coagulation and sand filtration were investigated. The effect of variable filtration media was also examined. In addition, the use of an activated carbon column was considered, and the effect of different retention times was evaluated. Results of this study showed that chemical coagulation using alum and Nalco removed only 32% of the total hydrocarbons and 80% of turbidity. Use of sand and a mixture of anthracite and sand filters showed additional removal of hydrocarbons and turbidity during the continuous filtration process. Increasing the anthracite depth relative to the total effective filtration depth increases the efficiency of the filter. Adsorption on granular activated carbon was shown to be an effective means for the removal of hydrocarbons. Results obtained indicated that the carbon adsorption capacity increases linearly as the retention time increases.     

不同养殖模式池塘沉降颗粒营养物质组成特征

2012年4~10月采用自制沉降颗粒收集装置收集主养草鱼和黄颡鱼池塘生态系统中沉降颗粒物,开展了颗粒物质的垂直沉降量以及沉降颗粒中碳氮磷等营养物质的组成及沉降通量的季节变化特征的研究。结果表明:养殖可以显著提高池塘颗粒物质的垂直沉降量,主养草鱼池塘中颗粒物质垂直沉降量显著高于主养黄颡鱼池塘(p0.01),且两种养殖模式池塘颗粒物质沉降量随着养殖时间推进有显著增加的趋势。主养草鱼的池塘中颗粒物质垂直沉降量在100.39~414.66g/(m2·d)之间变化,平均为224.46g/(m2·d),主养黄颡鱼池塘中沉降颗粒物质垂直沉降量在34.14~272.91g/(m2·d)之间变化,平均为155.18g/(m2·d)。两种养殖模式沉降颗粒的碳氮磷成分在养殖周期内的变化规律不明显但具有相似的变化趋势,主养黄颡鱼池塘沉降颗粒中TN、TC、TOC和TON的含量均比同时期主养草鱼高,且均随着养殖时间的推进,沉降颗粒中碳氮磷的总量呈增加趋势。两种养殖模式池塘沉降颗粒中的C/N比值与沉积物中的C/N比值较为接近,表明沉降颗粒与沉积物营养物质来源具有一定的相似性,同时养殖系统内养殖对象与其所处环境的相互依存和相互影响对颗粒物质的产生以及沉降具有重要作用。     

神农架大九湖泥炭地孔隙水溶解有机碳特征及其影响因素

溶解性有机碳（Dissolved Organic Carbon, DOC）是泥炭地碳循环的重要组成部分。以往的研究大多集中在北方泥炭地,而对亚热带季风区泥炭地DOC动力学的认识十分有限。利用紫外可见光光谱（UV-Vis）和三维荧光光谱结合平行因子分析法（EEM-PARAFAC）研究了神农架大九湖泥炭地孔隙水的DOC浓度与化学组成及其影响因素。EEM-PARAFAC的结果表明：大九湖泥炭地孔隙水DOC主要包含3种类腐殖质组分。紫外可见光和荧光指标表明,泥炭孔隙水DOC表观分子较小,而芳香度较高。深度剖面数据表明,泥炭孔隙水DOC浓度随深度降低,0~10 cm深度浓度最高为24.16 mg/L,150~160 cm深度浓度最低为9.72 mg/L,并且深层DOC以微生物代谢产生的新鲜有机物为主,具有较低的腐殖化度。此外,氧化还原电位（ORP）与DOC浓度及化学性质关系密切。以上结果表明,在亚热带泥炭地中,微生物来源或受微生物改造的有机物是泥炭孔隙水DOC的重要组成部分;垂向输送或选择性保存是影响该亚热带亚高山泥炭地DOC动力学的重要因素。     

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.     

Basic characterization of reference NOM from Central Europe — Similarities and differences

The FA and HA fractions represent 20 to 50% of the DOC of the original samples, depending on the origin, and serve as reference materials. The original aqueous samples and the aqueous solutions of the reference materials were characterized with methods suited for measuring samples at natural concentrations. The DOC normalized values of the spectral absorbances (λ = 254 nm; λ = 436 nm) in the original water samples were highest for the brown water and brown coal water and lowest for the secondary effluents. The FA fractions were similar in the UV-absorbance with the exception of the low-absorbing groundwater FA, reflecting a low density of double bonds. The DOC-normalized proton capacity of the FA fractions (10 to 20 μmol/mg) was highest for the brown coal, brown water, and soil-derived samples and again lowest for the groundwater FA. The high values are due to a higher contribution of the weak acids of phenolic type. Specific data for copper complexation capacity (0.5 to 2.5 μmol/mg) went parallel to the proton capacity. The characterization of the FAs by gel chromatography with organic carbon detection revealed three major fractions. The refractory part at short retention time dominated in the brown water and soil-derived samples, whereas the fractions for the lower molecular mass acids at long retention times were dominant in the secondary effluent and the brown coal isolate. Comparison with UV-detected chromatograms revealed a strong decrease in the specific absorbance of the secondary effluent. Up to 3% of the total mass of the FAs could be identified as hydrolyzable amino acids with the highest yield in the sample from secondary effluent and the lowest one in the groundwater sample. The nitrogen content was always higher in the FAs compared to the HAs of the same origin. The application of gel chromatography fluorescence and fluorescence decay time distribution analysis turned out to be a useful tool to differentiate between the different fractions of NOM, the isolates obtained by different methods (e.g., XAD-8, membrane separation) and the fractions of the samples from different origin and age. This is of special value, for the information can also be obtained for samples with natural NOM concentrations, even though further investigations required for full understanding of the data. This work is part of a multi-disciplinary research program (ROSIG: Refraktäre Organische Säuren in Gewässern), funded by the German Research Association (DFG).     

Association of organic matter, iron and inorganic phosphorus in lake waters

Gel permeation chromatography was used to fractionate ³²PO₄³⁻ labelled components by molecular size in filtered, destabilized lake foam, concentrated lake water, and lake sediment extracts. Evidence is presented for the abiotic formation of organic matter iron inorganic P complexes in lake foam, water and sediments. ³²PO₄^staggered was found to excahnge with low molecular weight, dissolved P fraction, probably an organic matter -Fe- inorganic P complex, but not with a high molecular weight, non-inorganic dissolved reactive P pool, hypothesized to be similar to the dimer. Our experiments suggest that inorganic P binding by high molecular weight organic matter may play a significant role in the P cycle. If the bound P is unavailable to algae and bacteria, the complexes could explain Rigler's (1968) hypothesis that the molybdenum blue technique may overestimate the free orthophosphate concentration by 10–100 times.     

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.