Influence of eutrophication on the coagulation efficiency in reservoir water

Water from the three reservoirs, Min-ter, Li-yu-ten and Yun-ho-shen, was examined for concentration of chlorophyll a, ultraviolet absorption (UV(254)), fluorescence intensity (FI), concentration of dissolved organic carbon (DOC), and fractionation of dissolved molecules by molecular weight. The water samples were collected over the change from spring to summer (May to July but before the typhoon season) when the water temperature and extent of eutrophication increase. Analytical results indicate that the concentration of DOC is proportional to the concentration of chlorophyll a, but not to the values of UV(254) and FI. Therefore, eutrophication, extraneous contaminants of small molecules, and the extracellular products of algae cause an increase in DOC, but a decrease in the proportion of large organic molecules such as of humic substances. The fraction of DOC with a molecular weight of less than 5000 Da increases with the concentration of chlorophyll a. All these data suggest that changes in the quality of water after eutrophication make the treatment of drinking water more difficult. The method of enhanced coagulation was recently developed for removing DOC. However, the results of this paper demonstrate that the efficiency of DOC removal falls as the degree of eutrophication increases. When the percentage of DOC with small molecules excreted by algae increased by 1%, the efficiency of DOC removal decreased by approximately 1%, implying that enhanced coagulation are not able to remove the DOC excreted by the algae during eutrophication, and resulting an increased concentration of trihalomethanes formation in water disinfections process.     

A comparative characterization of dissolved organic matter by means of original aqueous samples and isolated humic substances

The aim of our study is to test the use of less time-consuming spectroscopic methods applied on original water samples in order to obtain information about DOM composition without any sample preparation. These results were directly compared with results from a conventional isolation and characterization procedure of dissolved humic substances (fulvic acids – FA) isolated from the same water sample. FAs were characterized by UV-, fluorescence-, FTIR spectroscopy and elemental composition. UV absorbance and fluorescence behavior of FAs and original water samples follow the same pattern. A lower UV absorbance and a lower humification index (derived from the synchronous fluorescence spectra) of about 15% is typical for water samples compared to the FAs. We computed linear relationships between properties of the original water sample (UV-, synchronous fluorescence spectra) and the isolated FA (IR absorption, C/N ratio). The application of synchronous fluorescence and UV spectroscopy of aqueous samples has been proved to result in similar information about DOM composition as the characterization of isolated humic substances concerning the content of aromatic structures and the degree of humification.     

Monitoring of effluent DOM biodegradation using fluorescence, UV and DOC measurements

The potential of effluent DOM to undergo microbial degradation was assessed in batch experiments. Effluent samples from Haifa wastewater treatment plant and Qishon reservoir (Greater Haifa wastewater reclamation complex, Israel) were incubated either with effluent or soil microorganisms for a period of 2-4 months and were characterized by dissolved organic carbon contents (DOC), UV(254) absorbance and by fluorescence excitation-emission matrices. Three main fluorescence peaks were identified that can be attributed to humic/fulvic components and "protein-like" structures. During biodegradation, specific fluorescences (F/DOC) of the three peaks were increased at various extents, suggesting selective degradation of non-fluorescing constituents. In some cases increase in the effluent fluorescence (F) was observed thus proposing (i) the formation of new fluorescing material associated with DOM biodegradation and/or (ii) degradation of certain organic components capable of quenching DOM fluorescence. Based on the ratio between fluorescence intensity and UV(254), different biodegradation dynamics for fluorescent DOM constituents as compared with other UV-absorbing molecules was delineated. Overall, about 50% of the total DOM was found to be readily degradable such that residual resistant DOC levels were between 8 and 10 mg l(-1). Enhanced levels of residual DOM in effluent-irrigated soils may contribute to the DOM pool capable of carrying pollutants to groundwater.     

不同工艺对含高浓度腐殖酸地下水处理的可行性

针对内蒙古农村地区高腐殖酸地下水的处理问题，分别对（pH调节）-PAC强化混凝、高锰酸钾预氧化／混凝、活性炭吸附／混凝、Fenton氧化等技术处理的可行性进行了研究，同时利用三维荧光和高效体积排阻色谱分析处理前后水中有机物的组成变化特征。有机分析结果显示，水中的有机物为腐殖酸类物质，分子量分别为1600和3500，腐殖酸类物质为水中色度的主要贡献者。原水PAC强化混凝、高锰酸钾预氧化／PAC混凝对有机物的去除效果不佳，处理前后水样DOC浓度无明显变化，而pH调节．PAC强化混凝、微米活性炭吸附和Fenton氧化均能有效去除有机物。将原水pH调节至6．5，经300mg／LPAC混凝后出水DOC降至5．99mg／L。活性炭投加量为0．6g／L时，DOC降至7．6mg／L，然后采用60mg／LPAC混凝出去高度分散而不易沉降的小颗粒活性炭。此外，当反应初始pH值为3，过氧化氢投加量为0．5％（v／v），亚铁和双氧水摩尔比为0．05时，出水DOC降至5．6mg／L，氧化后有小分子有机物生成。     

土壤渗滤对有机微污染物去除性能研究

采用土壤柱试验研究了土壤渗滤对再生水中有机微污染物的去除性能。结果表明，土壤柱对再生水中的DOC、UV₂₅₄、总氮和总磷有较好的去除效果，并具有较高的抗冲击负荷的能力；土壤表层10 cm厚度对DOC的去除起主要作用；UV₂₅₄和AOX在土壤表层10 cm厚度降解效果不明显，随着深度增加去除率逐渐升高；液相色谱有机碳探测(LC-OCD)检测结果表明，土壤柱对溶解性有机物质的去除主要体现在对多糖物质的降解上，其次是有机酸类，对腐殖质也有一定的去除作用。     

UV-visible spectroscopy of organic carbon particulate sampled from ethylene/air flames

A systematic comparison of spectra obtained with extra and in situ diagnostics in the soot preinception region of rich, premixed ethylene air flames suggests that combustion generated organic carbon (OC) particulate can be extracted from flames and isolated from other flame material for further chemical analysis. Both the trend with height above the burner and the form of UV fluorescence and absorption spectra from extra situ sampled material captured in water agree with those measured in situ. These results show that the OC particulate formed in flames is partially water soluble. However, the collection efficiency can be increased using less polar solvents, like acetonitrile and dichloromethane. The fluorescence spectra from the water samples are comprised both a naphthalene-like component and a broad band UV fluorescence component similar to that observed in situ which is attributed to flame generated OC particulate. The broad band UV fluorescence centered around 320 nm is also observed very early in flames and does not change considerably with increasing flame residence time. These results support previous hypotheses that the UV broad band fluorescence is from carbonaceous material comprised two-ring aromatics, formed earlier than soot in the flame, and is still present along with soot at higher heights or flame residence times.     

Quantity and spectroscopic properties of soil dissolved organic matter (DOM) as a function of soil sample treatments: air-drying and pre-incubation

The dissolved organic matter (DOM) in soils is essentially defined by the way in which it is obtained. Therefore, we need to understand as to how pre-treatment of a soil will affect the characteristics of DOM, since this fraction may be strongly influenced by a soil's water content. The effect of two different pre-treatments on DOM from the A-horizons of a large variety of ecosystems and regions were compared. In both cases the soils were allowed to air-dry. In one case the air-dried soil was directly extracted (AD), while in the other case it was preincubated for 1 week at 50% of its water holding capacity (INCU). AD is simpler, but INCU brings the soil, and especially its microbial population, back to a standardised state, which is more representative of the usual state in the field. Both methods are used whenever an adjustment of the soil water content is essential to compare different regions or to eliminate short term weather effects. A significant regression indicated that the dissolved organic carbon (DOC) extracted from INCU samples was only 20% of AD DOC. Both the absorptivity (UV absorption divided by DOC) of 86% of the samples, and a fluorescence emission spectrum based Humification Index in all cases increased as a result of preincubation. This would indicate that labile compounds released during drying were metabolised during the incubation. However, the magnitude of this increase varied, and no correlation with soil organic and microbial carbon, pH, or texture could be detected. The results show that DOM extracted from AD and INCU soils is not comparable and that the differences are mainly due to the impact of air-drying on the microbial activity.     

Analysis of exhausts emitted by i.c. engines and stationary burners, by means of u.v. extinction and fluorescence spectroscopy

Optical investigations of the exhausts emitted by internal combustion (i.c.) engines and a stationary burner were performed, in order to assess their relative role as sources of organic matter to the atmosphere. Extinction spectra of air-diluted exhausts in the 200-400 nm u.v. band reveal the expected existence of gaseous trace-species (NO, NO2 and SO2) and carbonaceous particulate matter (soot). In addition, after subtracting the absorption contribution from known species, a strong residual absorption band remains below 250 nm, which is attributed to organic aromatic matter, involving no more than two aromatic rings. A set of ex situ extinction and laser induced fluorescence (LIF) experiments were carried out on condensed combustion-water samples. Extinction measurements from the water samples show absorption spectra similar to those observed from air-diluted samples, which are attributed to low volatility organic compounds, as they are trapped in the condensed phase. Combining the indications of extinction data for both air-diluted and condensed samples, it is suggested that the absorbing species might be molecular clusters of one/two aromatic rings. LIF spectra from condensed samples evidence two fluorescence bands, centered above 300 and 400 nm, respectively, whose intensities correlate with the combustion regimes. Analogous optical analysis on rain samples, collected in an urban area, showed that rain absorption and fluorescence spectra are similar to those found in condensed exhaust samples, which is consistent with the prevailing contribution of i.c. engines to the urban air pollution. The combined experimental data suggest that the absorbing and fluorescent species trapped in the condensed samples are organic (aromatic) compounds, involving mostly one two aromatic rings structural units, since they do not absorb above 250 nm. The overall molecular weight of the trapped material is likely heavy as they show low volatility.     

Degradation of aquatic humic material by ultraviolet light

Natural humic water was treated with ultraviolet (UV) light and UV + hydrogen peroxide (UV/H₂O₂. The effects on the dissolved organic carbon content (DOC), the UV-absorbance at 254 nm (UV-abs.), the molecular size distribution, pH, and mutagenic activity were monitored, and the identity and concentrations of the most abundant gas chromatographable organic degradation products were determined.

The DOC content and the UV-abs. of the water decreased substantially during treatment with UV/H₂O₂. The decreases were dependent on the time of irradiation (UV dose) as well as on the H₂O₂ dose applied. The humus macromolecules were degraded to smaller fragments during irradiation. At higher UV doses, however, part of the dissolved organic matter (DOM) was found to precipitate, probably as a result of polymerization. Oxalic acid, acetic acid, malonic acid, and n-butanoic acid were the most abundant degradation products detected. These acids were found to account for up to 20% and 80% of the DOM in UV- and UV/H₂O₂-treated waters, respectively. No mutagenic activity was generated by the UV irradiation or the UV/H₂O₂ treatment. It is further concluded that the substantial mutagenic activity formed during chlorination of humic waters cannot be decreased by using UV irradiation as a pretreatment step.     

Spectral attenuation of solar ultraviolet radiation in humic lakes in Central Finland

The attenuation of solar ultraviolet (UV) radiation in five lakes in Central Finland was evaluated through field measurements and/or by determining the optical properties of the lake water during summer 1999. Spectral UV irradiance in the air and at several depths underwater was measured in three lakes (Lake Palosj?rvi, Konnevesi, and Jyv?sj?rvi) with dissolved organic carbon (DOC) ranging from 4.9 to 8.7 mg l(-1) and chlorophyll a ranging from 1.6 to 16 g l(-1). According to the field measurements, 99% of the UV-B radiation was attenuated in approximately a half meter water column in the clearest lake. In the UV-A region at 380 nm, the corresponding attenuation occurred in the upper one meter. In a small humic lake (DOC 13.2-14.9 mg l(-1)) UV-B radiation was attenuated to 1% of the subsurface irradiance within the top 10 cm water column, whereas UV-A radiation (at 380 nm) penetrated more than twice as deeply (maximum 25 cm), as predicted from the absorption coefficients. These results suggest the importance of the dissolved fraction of lake water in governing the UV attenuation in lakes. This was seen from the significant relationship between the vertical attenuation coefficients (Kd) based on field measurements and the absorption coefficients (ad) derived from spectrophotometric laboratory scannings, as well as between Kd and DOC.     

Characterization and microbial utilization of dissolved organic carbon in groundwater contaminated with chlorophenols

The aim of this study was to characterize the labile part of dissolved organic carbon (DOC) present in groundwater by identification of natural organic carbon substrates and to assess their microbial utilization during aeration of the groundwater. The studied chlorophenol (CP) contaminated groundwater contained 60-2650 micromoll(-1) of DOC of which up to 98.0% were CPs; 1.7% were low-molecular weight organic acids and 0.2% were dissolved free amino acids. Traces of following natural organic carbon substrates were identified: L-alanine, L-isoleucine, L-leucine, L-serine, L-threonine, L-tyrosine, L-valine, L-aspartic, acetic, citric, formic, lactic, malic and oxalic acid. Dissolved oxygen concentration inside the CP-plume was lower (mean 25 micromoll(-1)) than outside of the plume (mean 102 micromoll(-1)). Over a monitoring period of four years the concentrations of CPs, Fe(II) and NH4+ were higher inside than outside of the CP-plume. Oxygen availability within the CP-plume limits in situ biological oxidation of CPs, DOC, NH4+ and Fe(II). The microbial enzymatic hydrolysis rates of 4-methylumbelliferyl and 7-amino-4-methylcoumarin-linked substrates varied from 0.01 to 52 micromoll(-1)h(-1) and was slightly higher inside than outside the plume. Microbial uptake rates of 14C-acetate, 14C-glucose and 14C-leucine were on average 28, 4 and 4 pmoll(-1)h(-1) outside and 17, 25 and 8 pmoll(-1)h(-1) inside the plume, respectively. The indigenous microorganisms were shown able of hydrolysis of dissolved organic matter, uptake and utilization of natural organic carbon substrates. Therefore, the labile part of DOC serves as a pool of secondary substrates beside the CP-contaminants in the groundwater and possibly help in sustaining the growth of CP-degrading bacteria.     

Carbonyl compounds and dissolved organic carbon in rainwater of an urban atmosphere

This study investigates the occurrence of carbonyl compounds in rainwater at the city of Thessaloniki, Northern Greece. The concentrations of carbonyl compounds (as sum of 14 compounds) ranged from 21.8 to 592 μg/L, mean concentration 119 μg/L. Formaldehyde, acetaldehyde, hexanal, glyoxal, and methylglyoxal were the dominant compounds. DOC concentrations in rainwater ranged from 0.46 to 21.3 mg/L. UV–Vis and fluorescence spectra characteristics showed variation among rain events. Carbonyl compounds were negatively correlated with temperature exhibited relatively higher concentrations in cold season. They also influenced by storm origin with higher concentrations under terrestrial air masses. Calm conditions enhance the concentrations of DOC. Wash out is an effective removal mechanism of DOC.     

Chemical characteristics of chromophoric dissolved organic matter in rainwater

Proton nuclear magnetic resonance (¹H-NMR), UV absorbance and excitation-emission matrix (EEM) fluorescence spectroscopy were used to define the chemical characteristics of chromophoric dissolved organic matter (CDOM) in whole and C₁₈ extracted rainwater. The average total recovery of fluorescence determined from the sum of extract and filtrate fractions relative to the whole was 86% suggesting that 14% of fluorescent CDOM in rainwater is comprised of very hydrophobic material that cannot be eluted from the column. Half the fluorescence of rainwater was recovered in the filtrate fraction which is important because it suggests that 50% of the chromophoric material present in precipitation is relatively hydrophilic. The average spectral slope coefficient was smaller in extracted samples (16.3 ± 9.0 μm^?1) relative to whole samples (18.9 ± 2.8 μm^?1) suggesting that the extracted material contains larger molecular weight material. Approximately one-third of the total dissolved organic carbon (DOC) in rainwater exists in the extract fraction suggesting that a large percentage of the uncharacterized DOC in rainwater can be accounted for by these hydrophobic macromolecular species. The fluorescence of extracted samples is strongly correlated with total NMR integration and is most sensitive to aromatic protons suggesting that molecules in this region are the most important in controlling the optical properties of rainwater. The lower removal efficiency of CDOM in rainwater relative to surface waters or the water-soluble fraction of aerosols during solid phase extraction (SPE) suggests that rainwater contains significantly more hydrophilic chromophoric compounds which are compositionally different than found in these other aquatic matrices.     

Seasonal changes in the chemical composition and reactivity of dissolved organic matter at the land-ocean interface of a subtropical river

Dissolved organic matter (DOM) is a critical component in aquatic ecosystems, yet its seasonal variability and reactivity remain not well constrained. These were investigated at the land-ocean interface of a subtropical river (Minjiang River, SE China), using absorption and fluorescence spectroscopy. The annual export flux of dissolved organic carbon (DOC) from the Minjiang River (5.48 × 10¹⁰ g year^?1) was highest among the rivers adjacent to the Taiwan Strait, with 72% occurring in spring and summer. The freshwater absorption coefficient a₂₈₀, DOC-specific UV absorbance SUVA₂₅₄ and humification index HIX were higher, while the spectral slope S_275–295 and biological index BIX were lower in summer than in winter. This suggests intensified export of terrestrial aromatic and high molecular weight constituents in the rainy summer season. Six fluorescent components were identified from 428 samples, including humic-like C1–C3, tryptophan-like C4 and C6, and tyrosine-like C5. The freshwater levels of four components (C1, C2, C4, and C6) were lower while that of C5 was higher in the wet season than in the dry season, suggesting contrasting seasonal variations of different constituents. Laboratory experiments were performed to assess the effects of photochemical and microbial degradation on DOM. Photo-degradation removed chromophoric and fluorescent DOM (CDOM and FDOM) effectively, which was stronger (i) for high molecular weight/humic constituents and (ii) during summer under higher solar radiation. Microbial degradation under laboratory controlled conditions generally showed little effect on DOC, and had smaller impact on CDOM and FDOM in winter than in summer. Overall, this study showed notable seasonal changes in the chemical composition and reactivity of DOM at the land-ocean interface, and demonstrated the significant effects of photo-degradation.

     

Differentiating with fluorescence spectroscopy the sources of dissolved organic matter in soils subjected to drying

The relative fluorescence, normalised on dissolved organic carbon (DOC), and a humification index, based on the location of the fluorescence emission spectra, were used to investigate the possible sources of the increase in dissolved organic matter (DOM) when a soil is dried. From these 2 parameters it could be seen that air drying resulted in a minor increase of more humified material in DOM while the effect of oven drying was mainly due to cell lysis.     

Seasonal and air mass trajectory effects on dissolved organic matter of bulk deposition at a coastal town in south-western Europe

Rainwater contains a complex mixture of organic compounds which may influence climate, terrestrial and maritime ecosystems and thus human health. In this work, the characteristics of DOM of bulk deposition at a coastal town on the southwest of Europe were assessed by UV–visible and three-dimensional excitation–emission matrix fluorescence spectroscopies and by dissolved organic carbon (DOC) content. The seasonal and air mass trajectory effects on dissolved organic matter (DOM) of bulk deposition were evaluated. The absorbance at 250 nm (UV_250nm) and integrated fluorescence showed to be positively correlated with each other, and they were also positively correlated to the DOC in bulk deposition, which suggest that a constant fraction of DOM is likely to fluoresce. There was more chromophoric dissolved organic matter (CDOM) present in summer and autumn seasons than in winter and spring. Bulk deposition associated with terrestrial air masses contained a higher CDOM content than bulk deposition related to marine air masses, thus highlighting the contribution of terrestrial/anthropogenic sources.     

Tracking the spectroscopic and chromatographic changes of algal derived organic matter in a microbial fuel cell

Changes in the characteristics of algae-derived organic matter (AOM) were examined upon the operation of a microbial fuel cell (MFC) using multiple analytical methods. Temporal variations in the UV absorption and fluorescence excitation–emission matrix of the AOM revealed that less condensed humic-like components and large-sized protein-like fluorescent compounds were preferentially decomposed over the period of electricity generation. They also showed that low UV-absorbing extracellular organic matters (EOM) were produced at the end of the operation. SEC chromatograms demonstrated that smaller-sized UV-absorbing components were initially decomposed, followed by the net production of EOM with an intermediate molecular weight. Fourier transform infrared (FT-IR) spectra showed that proteins and polysaccharides were the two most dominant structures of the AOM in the MFC. Two-dimensional correlation spectroscopy combined with FT-IR provided additional valuable information on the sequential changes of the AOM, which occurred in the order of proteins → acidic functional groups → polysaccharides → amino acids/proteins.     

Absorption and fluorescence properties of chromophoric dissolved organic matter: implications for the monitoring of water quality in a large subtropical reservoir

The development of techniques for real-time monitoring of water quality is of great importance for effectively managing inland water resources. In this study, we first analyzed the absorption and fluorescence properties in a large subtropical reservoir and then used a chromophoric dissolved organic matter (CDOM) fluorescence monitoring sensor to predict several water quality parameters including the total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD), dissolved organic carbon (DOC), and CDOM fluorescence parallel factor analysis (PARAFAC) components in the reservoir. The CDOM absorption coefficient at 254 nm (a(254)), the humic-like component (C1), and the tryptophan-like component (C3) decreased significantly along a gradient from the northwest to the lake center, northeast, southwest, and southeast region in the reservoir. However, no significant spatial difference was found for the tyrosine-like component (C2), which contributed only four marked peaks. A highly significant linear correlation was found between the a(254) and CDOM concentration measured using the CDOM fluorescence sensor (r ²?=?0.865, n?=?76, p?相似文献   

Influence of soil conditions on dissolved organic matter leached from forest and wetland soils: a controlled growth chamber study

This study investigated the effects of various soil conditions, including drying-rewetting, nitrogen deposition, and temperature rise, on the quantities and the composition of dissolved organic matter leached from forest and wetland soils. A set of forest and wetland soils with and without the nitrogen deposition were incubated in the growth chambers under three different temperatures. The moisture contents were kept constant, except for two-week drying intervals. Comparisons between the original and the treated samples revealed that drying-rewetting was a crucial environmental factor driving changes in the amount of dissolved organic carbon (DOC). The DOC was also notably increased by the nitrogen deposition to the dry forest soil and was affected by the temperature of the dry wetland soil. A parallel factor (PARAFAC) analysis identified three sub-fractions of the fluorescent dissolved organic matter (FDOM) from the fluorescence excitation–emission matrices (EEMs), and their compositions depended on drying-rewetting. The data as a whole, including the DOC and PARAFAC components and other optical indices, were possibly explained by the two main variables, which were closely related with the PARAFAC components and DOC based on principal component analysis (PCA). Our results suggested that the DOC and PARAFAC component information could provide a comprehensive interpretation of the changes in the soil-leached DOM in response to the different environmental conditions.     

Fluorescence and DOC contents of estuarine pore waters from colonized and non-colonized sediments: effects of sampling preservation

The influence of the colonization of salt marsh sediments with Halimione portulacoides was evaluated by analysing the fluorescent dissolved organic matter (FDOM) in sediment pore waters from a salt marsh at different depths. Cores of sediments at colonized and non-colonized sites were collected from a coastal lagoon (Ria de Aveiro, Portugal). The DOC content of extracted pore waters was determined and characterized by synchronous molecular fluorescence (Deltalambda=60nm) and UV-visible spectroscopies. The common practice of freezing sediment cores for further and later chemical investigation was shown not to be an appropriate methodology of sample preservation. On the contrary, freezing of extracted and filtered pore water seemed not to affect either the DOC content or the fluorescence properties of pore waters. Two types of fluorescent substances were found in the pore waters spectra; one corresponding to humic-like substances and another one resembling proteins. However, major differences were found in the spectra of pore waters depending on both depth and the presence/absence of vegetation colonization.