Multistep, microvolume resin fractionation combined with 3D fluorescence spectroscopy for improved DOM characterization and water quality monitoring

Conventionally, resin fractionation (RF) method has been widely used to characterize dissolved organic matter (DOM) found in different source waters based on general and broad DOM fractions grouping. In this study, a new refined method using multistep, microvolume resin fractionation combined with excitation emission matrix fluorescence spectroscopy (MSM-RF-EEMS) was developed for further isolation and characterization of subfractions within the primary DOM fractions separated from using the conventional RF method. Subsequently, its feasibility in indicating the occurrence of urban pollution in source waters was also assessed. Results from using the new MSM-RF-EEMS method strongly illustrated that several organic subfractions still exist within the regarded primary pure hydrophobic acid (HoA) fraction including the humic- and fulvic-like organic matters, tryptophan- and tyrosine-like proteins. It was found that by using the MSM-RF-EEMS method, the organic subfractions present within the primary DOM fraction could be easily identified and characterized. Further validation on the HoA fraction using the MSM-RF-EEMS method revealed that the constant association of EEM peak T1 (tryptophan) fraction could specifically be used to indicate the occurrence of urban pollution in source water. The correlation analysis on the presence of EEM peak T2 (tyrosine) fraction could be used as a supplementary proof to further verify the presence of urban pollution in source waters. These findings on using the presence of EEM peaks T1 and T2 within the primary HoA fraction would be significant and useful for developing a sensory device for online water quality monitoring.     

七虎林河流域上游溶解性有机质光谱特性分析

七虎林河源头区地表腐殖质随着径流的冲刷进入水体,形成了天然有机质(NOM),其中,溶解性有机质(DOM)易对河流水质造成影响。为了研究七虎林河中DOM的时空分布特征及其对水质的影响,开展了6次采样,分析了水体及土壤吸收光谱和荧光光谱特征参数,利用平行因子(PARAFAC)算法解析了水体DOM的特性及来源。结果表明：七虎林河上游水体五日生化需氧量(BOD₅)、高锰酸盐指数(COD_Mn)、化学需氧量(COD)、可溶性有机碳(DOC)的浓度分别为1.4 mg/L±0.2 mg/L、6.1 mg/L±3.0 mg/L、21 mg/L±8 mg/L、7.0 mg/L±3.2 mg/L,BOD₅/COD平均值为0.08,说明流域内水体DOM的可生化性差,对水质影响较小。光谱特征参数紫外吸收系数(SUVA₂₅₄)、荧光指数(FI)、腐殖化指数(HIX)、生物源指数(BIX)分析结果表明,七虎林河上游云山水库库上林区河段DOM的物质组成与水库及库下河段差异显著。库上河段DOM的芳香碳含量更高、分子量更大、自生源组分...     

城市雨水管网沉积物不同分子量溶解性有机质空间分布及光谱特征

采用超滤法、紫外-可见吸收光谱和三维荧光光谱分析法研究了北京市西城区4个典型功能区(居民区、文教区、交通区、商业区)雨水管网表层沉积物中不同分子量溶解性有机质(DOM)的分布特征和光谱特性。结果表明:雨水管网沉积物DOM以小分子量组分为主,约占整体水平的60%~70%。通过分析还发现,沉积物中小分子量(小于3k Da)DOM主要是类蛋白物质,而腐殖类物质主要集中在DOM的大分子量(大于10k Da)区域,微生物活动对小分子量DOM贡献作用显著,由此可见,DOM的分子组成和结构特性在一定程度上可以作为雨水管网沉积物DOM主成分和来源的衡量指标。4个功能区DOM腐殖化水平较低,表现出随分子量增大DOM腐殖化程度升高的规律。     

紫外光诱导荧光分析仪结合多元线性回归算法在城市河流常规污染指标监测中的应用

为建立一种针对城市河流水体常规污染指标的快速原位监测方法,首次运用紫外光诱导荧光分析仪对扬州市60条城市河流进行水体三维荧光光谱(EEM)测量,形成了具有多样性的水质样本集合.利用峰值拾取法、相关性分析和主成分分析3种方式从三维荧光光谱中提取溶解性有机物(DOM)污染信息,结合多元线性回归算法(MLR),建立与化学需氧...     

城市垃圾填埋场渗滤液中污染物检测与分析

垃圾渗滤液水质复杂,危害性大,对其无害化处理尚未得到很好解决。溶解性有机物(DOM)是导致渗滤液处理难以达标的主导性污染物。采用GC-MS技术可将渗滤液中DOM标识划分为亲水性和疏水性两类物质,为DOM的针对性处理提供了新的思路。采用ICP-AES从渗滤液中检测出美国环境保护局颁布的13种优先污染重金属中的11种,其含量大幅超标。废弃的电子材料、颜料涂料、电池以及药物等物质的不分类收集是导致渗滤液中重金属浓度超标、毒性增强的主要原因。在垃圾渗滤液处理领域,认为BOD5/COD小于0.3就不可以采用生物法处理的传统观点已经不符合实验与工程现实。通过检测与分析,掌握了垃圾渗滤液的水质特性与污染源头,能够为制定切实可行的处理方案提供借鉴。     

Profiling and monitoring of DOM in brewery wastewater and treated wastewater

Dissolved organic matter (DOM) in raw and treated wastewater from two breweries in Thailand was profiled and monitored for the purpose of water reclamation. The wastewater and the effluent from the use of an upflow anaerobic sludge blanket (UASB) and activated sludge (AS) were collected and analyzed through a resin fractionation method using the fluorescent excitation?Cemission matrix (FEEM) technique. The results revealed that the major organic fractions in the brewery wastewater were hydrophobic acid (HPOA) and hydrophilic base (HPIB), accounting for 65% of total dissolved organic carbon (DOC) mass for brewery A and 56% of total DOC mass for brewery B. The FEEM results indicated that the organic matter in the wastewaters of both breweries were mainly composed of tryptophan-like substances, represented by peaks C (230 nm_Ex/340?C365 nm_Em) and D (265?C295 nm_Ex/315?C390 nm_Em), and humic-like substances, represented by peaks E (290 nm_Ex/400 nm_Em), F (330?C335 nm_Ex/395?C410 nm_Em), and G (255?C265 nm_Ex/435?C455 nm_Em). The analysis revealed that the reduction of DOM occurred mostly during the UASB treatment where most of the DOM reduction resulted from the removal of the HPOA and HPIB fractions. The HPOA fraction, a group of humic-like substances, is of particular concern when reclaiming treated brewery wastewater, and although it was reduced by more than 80% of its initial amount, it was still a dominant DOM fraction in the effluents.     

Multivariate analysis for spatial distribution of dissolved organic matters in a large river-type dam reservoir

In contrast to extensive studies of dissolved organic matters (DOM) in natural lakes, the distributions and the characteristics of DOM in artificial dam reservoirs have not been well documented despite a growing demand for the construction worldwide. For this study, spatial variations in the concentrations and the characteristics of DOM in Lake Paldang, a large river-type dam reservoir, were investigated using the concentrations, the specific UV absorbance (SUVA), the synchronous fluorescence spectra and the molecular weight (MW(w)) values. In addition, environmental factors determining the DOM spatial distribution were examined based on a principal component analysis (PCA). Variations in the DOM characteristics were greater than those for the concentrations (1.1-2.4 mg C/L). In contrast to typical lakes, vertical variations with a depth were much smaller than those observed among horizontal sampling sites within the reservoir. Irrespective of the depth, four individual sampling locations were easily distinguished by comparison of some selected DOM characteristics. The protein-like fluorescence (PLF), MW(w) and SUVA values observed at the location near the dam exceeded the corresponding values for the sampling locations near major influent rivers, suggesting that, even for the river-type dam reservoir, the downstream DOM characteristics may be governed by in-lake DOM production processes such as the release from sediments and algal activities. The results of principal component analysis (PCA) revealed that approximately 61% of the variance in DOM distribution might be explained by allochthonous/autochthonous carbon sources and predominant presence of either total nitrogen or total phosphorous over the other.     

Size and resin fractionations of dissolved organic matter and trihalomethane precursors from four typical source waters in China

Dissolved organic matter (DOM) and its potential to form disinfection by-products (DBPs) during drinking water treatment raise challenges to water quality control. Understanding both chemical and physical characteristics of DOM in source waters is key to better water treatment. In this study, the DOM from four typical source waters in China was fractionated by XAD resin adsorption (RA) and ultrafiltration (UF) techniques. The trihalomethane formation potential (THMFP) of all fractions in the DOM were investigated to reveal the major THM precursors. The fraction distributions of DOM could be related to their geographical origins in a certain extent. The dominant chemical fraction as THM precursors in the DOM from south waters (East-Lake reservoir in Shenzhen and Peal rivers in Guangzhou) was hydrophobic acid (HoA). The size fraction with molecular weight (MW) <1 kDa in both south waters had the highest THMFP. The results of cluster analysis showed that the parameters of fractions including DOC percentage (DOC%), UV₂₅₄%, SUVA₂₅₄ (specific UV₂₅₄ absorbance) and THMFP were better for representing the differences of DOM from the studied waters than specific THMFP (STHMFP). The weak correlation between SUVA₂₅₄ and STHMFP for either size or XAD fractions suggests that whether SUVA₂₅₄ can be used as an indicator for the reactivity of THM formation is highly dependent on the nature of organic matter.     

Fluorescence spectroscopic characterization of dissolved organic matter fractions in soils in soil aquifer treatment

This work investigated the effect of soil aquifer treatment (SAT) operation on the fluorescence characteristics of dissolved organic matter (DOM) fractions in soils through laboratory-scale soil columns with a 2-year operation. The resin adsorption technique (with XAD-8 and XAD-4 resins) was employed to characterize the dissolved organic matter in soils into five fractions, i.e., hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N), and hydrophilic fraction (HPI). The synchronous fluorescence spectra revealed the presence of soluble microbial byproduct- and humic acid-like components and polycyclic aromatic compounds in DOM in soils, and SAT operation resulted in the enrichment of these fluorescent materials in all DOM fractions in the surface soil (0–12.5 cm). More importantly, the quantitative method of fluorescence regional integration was used in the analysis of excitation–emission matrix (EEM) spectra of DOM fractions in soils. The cumulative EEM volume (Φ _{T, n} ) results showed that SAT operation led to the enrichment of more fluorescent components in HPO-A and TPI-A, as well as the dominance of less fluorescent components in HPO-N, TPI-N, and HPI in the bottom soil (75–150 cm). Total Φ _{T, n} values, which were calculated as $ {\Phi_{{T,n}}} \times {\mathrm{DOC}} $ , suggested an accumulation of fluorescent organic matter in the upper 75 cm of soil as a consequence of SAT operation. The distribution of volumetric fluorescence among five regions (i.e., P _{i, n} ) results revealed that SAT caused the increased content of humic-like fluorophores as well as the decreased content of protein-like fluorophores in both HPO-A and TPI-A in soils.     

汉江下游干支流浮游植物群落特征及其对水质的指示评价

浮游植物群落的动态变化可以全面、真实地反映水质的优劣,有利于了解水体污染状况的发展趋势.为及时掌握汉江下游水质变化,基于2019年3—12月汉江下游干流及主要支流浮游植物和水体理化指标监测数据,分析了浮游植物群落结构特征,并通过冗余分析研究了影响浮游植物群落结构的主要环境因子,同时运用浮游植物群落特征对汉江下游水质进行...     

The development of a chemical 'fingerprint' to characterise dissolved organic matter in natural waters

A suite of twelve assays has been used to 'fingerprint' dissolved organic matter (DOM). The assays were applied directly to filtered natural water samples. Temperature, pH and conductivity accounted for the environmental conditions on-site. Bulk carbon characteristics were assayed by measuring UV absorbance at 200 and 240 nm, colour in grade Hazen, DOC (dissolved organic carbon), fluorescence (excitation 370 nm, emission 450 nm) and the complexation of phenol itself. Measuring hydroxybenzenes ('monophenolics'), polyhydroxybenzenes ('polyphenolics') and total phenolics with the Gibbs, Prussian Blue and Folin-Ciocalteau assays, respectively, determined the phenolics pool. The methodology was tested on six freshwater sites in North Wales chosen to provide differences in vegetation, land-use and water chemistry and sampled once during each season. A novel approach for the presentation of the data has been developed that combines all range normalised assay results for each site and each season within one polar plot, hence the term 'fingerprint'. The data was also analysed using principal component factor analysis. Assays characterised as determining the chemical properties of DOM contributed to Factor 1 and explained 59% of the variation in the data. Assays apparently determined by the water matrix, contributed to Factor 2 and explained 20% of the variation within the data. The factor scores obtained for each site showed more variation for assays relating to the chemical properties of DOM than to the surrounding water matrix. The methodology was found to detect chemical changes within DOM for each site throughout the year and different responses for different sites.     

Water quality assessment and source identification of Daliao river basin using multivariate statistical methods

Multivariate statistical methods, such as cluster analysis (CA), discriminant analysis (DA) and principal component analysis (PCA), were used to analyze the water quality dataset including 13 parameters at 18 sites of the Daliao River Basin from 2003-2005 (8424 observations) to obtain temporal and spatial variations and to identify potential pollution sources. Using Hierarchical CA it is classified 12 months into three periods (first, second and third period) and the 18 sampling sites into three groups (groups A, B and C). Six significant parameters (temperature, pH, DO, BOD(5), volatile phenol and E. coli) were identified by DA for distinguishing temporal or spatial groups, with close to 84.5% correct assignment for temporal variation analysis, while five parameters (DO, NH(4)(+)-N, Hg, volatile phenol and E. coli) were discovered to correctly assign about 73.61% for the spatial variation analysis. PCA is useful in identifying five latent pollution sources for group B and C (oxygen consuming organic pollution, toxic organic pollution, heavy metal pollution, fecal pollution and oil pollution). During the first period, sites received more oxygen consuming organic pollution, toxic organic pollution and heavy metal pollution than those in the other two periods. For group B, sites were mainly affected by oxygen consuming organic pollution and toxic organic pollution during the first period. The level of pollution in the second period was between the other two periods. For group C, sites were mainly affected by oil pollution during the first period and oxygen consuming organic pollution during the third period. Furthermore, source identification of each period for group B and group C provided useful information about seasonal pollution. Sites were mainly affected by fecal pollution in the third period for group B, indicating the character of non-point source pollution. In addition, all the sites were also affected by physical-chemistry pollution. In the second and third period for group B and second period for group C sites were also affected by natural pollution.     

Changes in the sorption and rate of 17β-estradiol biodegradation by dissolved organic matter collected from different water sources

The potential biodegradation and subsequent transformation of 17β-estradiol (E2) to estrone (E1) were examined in the presence of various dissolved organic matter (DOM) isolated from effluent, river and lake waters. In addition, estrogenicity was estimated in association with the removal of E2 via its sorption onto DOM and biodegradation. The more biodegradable lake-derived DOM promoted more extensive transformation of E2 into E1 than the effluent organic matter through a biodegradation process. Overall, under all conditions, biodegradation dominated the removal of E2 in water. The increased dissolved organic carbon (DOC) concentrations in river and lake-derived DOM (e.g. 6.5 mg C L(-1)) reduced the removal of E2 by decreasing its biodegradation due to the moderate sorption of E2 onto DOM. The effluent organic matter showed greater removal of E2 via biodegradation, as well as significantly high sorption. This was associated with a large amount of hydrophobic fulvic acid (FA)- and humic acid (HA)-like organic components, as shown by the small increase in the specific UV absorbance at 254 nm (SUVA(254)). An increase in the DOC concentration reduced the removal of E2, resulting in high estrogenicity. The present study suggests that both organic composition and DOC concentration influenced the removal of E2 and, therefore, should be fully considered when assessing estrogenicity and its impacts on the aquatic environment.     

Comparison of dissolved organic matter fractions in a secondary effluent and a natural water

This research compared the structural and chemical characteristics among dissolved organic matter (DOM) fractions within the same source and among different origins. Samples taken from the Taiping Wastewater Treatment Plant (TWTP) (Harbin, China) and from the Songhuajing River (SR), Heilongjiang Province, China were chosen to represent waters containing DOM of wastewater origin and of natural-water origin, respectively. DOM was fractionated using XAD resins into five fractions: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). The SR fractions were more UV-sensitive and more reactive with chlorine in formation of trihalomethanes (THMs) than the TWTP secondary effluent (TSE) fractions. The aromatic character peaks in the Fourier-transform infrared (FT-IR) spectra of SR fractions were clearer than those of TSE fractions. On the other hand, the peaks of carbohydrates in TSE fractions were more prominent in comparison with SR fractions. In addition, the amide-2 peak was present in the spectra of all the five TSE fractions but not visible in the spectra of SR fractions. The fluorescence results showed that SR DOM fractions contained more fulvic acid-like fluorescent compounds while TSE DOM fractions had higher amounts of protein-like fluorescent components.     

The chronic effects of oil pollution on marine phytoplankton in a subtropical bay, China

To evaluate the effects of crude oil water accommodated fraction (WAF) on marine phytoplankton community, natural phytoplankton collected seasonally from the Yueqing bay were exposed to eight groups of crude oil WAF for 15 days under laboratory conditions. Chlorophyll a and cell density were measured, and species of phytoplankton were identified every 24 h to reflect the change of phytoplankton community. The results showed that (1) High concentrations (??2.28 mg l^???1) of oil pollution would greatly restrain phytoplankton growth (p?< 0.001), decrease chlorophyll a content and cell density, whereas low concentrations (??1.21 mg l^???1) did not restrain its growth but rather promoted the phytoplankton growth. (2) The biodiversity, evenness, and species number of phytoplankton were all significantly influenced by crude oil WAF in all seasons (p?<?0.001). (3) The dominant species changes were different under different pollutant concentrations in different seasons. Different species had different tolerances to the oil pollution, thus leading to abnormal succession.     

Isolation and fractionation of natural organic matter: evaluation of reverse osmosis performance and impact of fractionation parameters

Dissolved organic matter (DOM) from three surface waters was isolated using reverse osmosis (RO) and subsequently fractionated using resin adsorption chromatography (RAC). Efficacy of RO was evaluated by closing mass balances for dissolved organic carbon (DOC). RAC was evaluated by investigating the effect of column operational parameters (column capacity factor, k', and solute initial concentration, C0) on DOM fractionation and subsequent disinfection by-product formation. Efficacy of RO was dependent on both isolation conditions and source water characteristics. In general, RO more effectively isolated DOM in high specific ultraviolet absorbance (SUVA254) water than low SUVA254 water, and showed higher DOM recovery at ambient pH (approximately 7) than at low pH (approximately 4). The fractionation of the isolated DOM indicated that the relative amount of the hydrophobic fraction decreased with increasing k', thus affecting the overall distribution of DOM. However, the distribution of DOM fractions was not influenced by varying C0 up to 150 mg l(-1) at k' of 15. The effect of k' on the formation and speciation of trihalomethanes (THM) and haloacetic acids (HAA) was not significant up to k' of 30.     

River discharge as a major driving force on spatial and temporal variations in zooplankton biomass and community structure in the Godavari estuary India

Variability in horizontal zooplankton biomass distribution was investigated over 13 months in the Godavari estuary, along with physical (river discharge, temperature, salinity), chemical (nutrients, particulate organic matter), biological (phytoplankton biomass), and geological (suspended matter) properties to examine the influencing factors on their spatial and temporal variabilities. The entire estuary was filled with freshwater during peak discharge period and salinity near zero, increased to ~ 34 psu during dry period with relatively high nutrient levels during former than the latter period. Due to low flushing time (< 1 day) and high suspended load (> 500 mg L^?1) during peak discharge period, picoplankton (cyanophyceae) contributed significantly to the phytoplankton biomass (Chl-a) whereas microplankton and nanoplankton (bacillariophyceae, and chlorophyceae) during moderate and mostly microplankton during dry period. Zooplankton biomass was the lowest during peak discharge period and increased during moderate followed by dry period. The zooplankton abundance was controlled by dead organic matter during peak discharge period, while both phytoplankton biomass and dead organic matter during moderate discharge and mostly phytoplankton biomass during dry period. This study suggests that significant modification of physico-chemical properties by river discharge led to changes in phytoplankton composition and dead organic matter concentrations that alters biomass, abundance, and composition of zooplankton in the Godavari estuary.     

钦州湾春季水质营养状况分析与评价

根据2010年4月对钦州湾海域调查结果,分析并评价了该海域春季的营养状况。结果表明,表层海水中DIN和SiO₃-Si都为茅尾海钦江入海口含量较高,PO₄-P为茅尾海西南部沿岸增养殖区含量较高,DIN、PO₄-P和SiO₃-Si水平分布上均表现为湾内含量高于湾外。从营养结构看,与Justic等提出的营养盐化学计量限制标准比较,符合P限制条件,PO₄-P可能成为浮游植物生长的潜在限制因子。根据营养状态指数评价模式和有机污染评价指数计算结果显示,2010年春季钦州湾海域营养水平属于中营养水平,有机污染程度属4级,表明钦州湾表层海水水质已达到中度污染。     

污染治理前后小清河上游浮游植物群落变化与水质评价

为研究小清河污染治理前后浮游植物群落与水质变化,分别于2015年(治理前)和2020年(治理后)在小清河上游进行采样调查。调查结果显示,2015年样品中共检出浮游植物6门35种,2020年样品中共检出4门31种。配对样本t检验结果显示,污染治理前后的浮游植物种类、密度都发生了显著改变。相比治理前,治理后的硅藻门和绿藻门相对丰度分别上升了51.6个百分点和13.3个百分点,蓝藻门下降了62.9个百分点,小环藻(Cyclotella spp.)取代微囊藻(Microcysitis spp.)成为绝对优势种,群落类型由蓝藻型演替为硅藻型。相似性分析结果和相似度百分比分析结果表明,小清河上游群落特征发生显著改变。非度量多维标度分析结果显示,治理后的S2与S3采样点群落特征表现出差异,S4与S1采样点群落特征相似。通过冗余分析发现,治理后,TP、DO对浮游植物群落的影响明显减弱,TN、NH₃-N、pH是目前影响群落特征的主要指标,主城区氮磷污染对浮游植物的影响范围由S2、S3、S4采样点缩小到S2采样点。治理前后的小清河上游Shannon-Wiener多样性指数、Pielou均匀度指数和Marglef丰富度指数存在显著差异。总体来看,治理后的小清河上游水质处于α-中污染状态,较治理前有明显改善。     

Assessment of seasonal variations of surface water quality characteristics for Porsuk Stream

In this study, the factor analysis technique is applied to surface water quality data sets obtained from Porsuk stream in Turkey, generated during 10 years (1995-2005) monitoring of 29 parameters at one site (Esenkara) for all four seasons. The varifactors obtained from factor analysis indicate that the parameters responsible for water quality variations are mainly related to mineral and inorganic nutrients, organic pollution, microbiological pollution in winter and spring; mineral and nutrients in summer; microbiological and nutrient pollution in fall. This study presents the necessity and usefulness of multivariate statistical assessment of large and complex databases in order to get better information about the quality of surface water.