High-frequency measurements reveal spatial and temporal patterns of dissolved organic matter in an urban water conveyance

Stormwater runoff in urban areas can contribute high concentrations of dissolved organic matter (DOM) to receiving waters, potentially causing impairment to the aquatic ecosystem of urban streams and downstream water bodies. Compositional changes in DOM due to storm events in forested, agricultural, and urban landscapes have been well studied, but in situ sensors have not been widely applied to monitor stormwater contributions in urbanized areas, leaving the spatial and temporal characteristics of DOM within these systems poorly understood. We deployed fluorescent DOM (FDOM) sensors at upstream and downstream locations within a study reach to characterize the spatial and temporal changes in DOM quantity and sources within an urban water conveyance that receives stormwater runoff. Baseflow FDOM decreased over the summer season as seasonal flows upstream transported less DOM. FDOM fluctuated diurnally, the amplitude of which also declined as the summer season progressed. During storms, FDOM concentrations were rapidly elevated to values orders of magnitude greater than baseflow measurements, with greater concentrations at the downstream monitoring site, revealing high contributions from stormwater outfalls between the two locations. Observations from custom, in situ fluorometers resembled results obtained using laboratory methods for identifying DOM source material and indicated that DOM transitioned to a more microbially derived composition as the summer season progressed, while stormwater contributions contributed DOM from terrestrial sources. Deployment of a mobile sensing platform during varying flow conditions captured spatial changes in DOM concentration and composition and revealed contributions of DOM from outfalls during stormflows that would have otherwise been unobserved.     

Spectroscopic Distribution of Dissolved Organic Matter in a Dam Reservoir Impacted by Turbid Storm Runoff

Spectroscopic characteristics of dissolved organic matter (DOM) in a large dam reservoir were determined using ultraviolet absorbance and fluorescence spectroscopy to investigate spatial distribution of DOM composition after turbid storm runoff. Water samples were collected along a longitudinal axis of the reservoir at three to four depths after a severe storm runoff. Vertical profiles of turbidity data showed that a turbid water layer was located at a middle depth of the entire reservoir. The spectroscopic characteristics of DOM samples in the turbid water layer were similar to those of terrestrial DOM, as demonstrated by the higher specific UV absorbance (SUVA) and the lower fluorescence emission intensity ratio (F ₄₅₀/F ₅₀₀) compared to other surrounding DOM samples in the reservoir. Synchronous fluorescence spectroscopy revealed that higher content of humic-like DOM composition was contained in the turbid water. Fluorescence excitation–emission matrix (EEM) showed that lower content of protein-like aromatic amino acids was present in the turbid water DOM. The highest protein-like fluorescence was typically observed at a bottom layer of each sampling location. The bottom water DOM exhibited extremely high protein-like florescence near the dam site. The particular observation was attributed to the low water temperature and the isolation of the local bottom water due to the upper location of the withdrawal outlet near the dam. Our results suggest that the distribution of DOM composition in a dam reservoir is strongly influenced by the outflow operation, such as selective withdrawal, as well as terrestrial-origin DOM inputs from storm runoff.     

Quantifying the phenolic content of freshwaters using simple assays with different underlying reaction mechanisms

Five different assays, Gibbs, Prussian Blue, Folin-Ciocalteau, fluorescence quenching of added phenol and precipitation of phenolics with bovine serum albumin (BSA) were investigated for their suitability in measuring the phenolic content of freshwaters. Phenol and a hydrolysable tannic acid were used as standards for monophenolics and polyphenolics, respectively. The individual and simultaneous application of both standards in doubly distilled water and filtered freshwater samples showed no matrix interference for the Gibbs, the Prussian Blue and the Folin-Ciocalteau assays. The quenching of phenol fluorescence and incomplete precipitation of added tannic acid in the freshwater samples were thought to originate from complexation. The Gibbs assay was specific for monophenolics, monohydroxybenzenes, with a Criterion of Detection (CoD) of 0.027 mg l(-1). Evaluating the assay using twenty-two monophenolics of lignin origin showed, apart from phenol itself, the phenolic acids vanillic, isovanillic, ferulic and syringic to have a linear response between 0 and 10 microM. The other monophenolics were not responsive in the Gibbs assay. The oxidation-based assays Prussian Blue and Folin-Ciocalteau had a CoD of 0.169 and 0.025 mg l(-1), respectively. The ratio of response of both assays for each sample was taken as an indication of the degree of polymerisation of the phenolic content. The Folin-Ciocalteau assay was used directly on the samples, on samples spiked with tannic acid at 2 and 4 mg l(-1), and after precipitation of phenolics with BSA. The difference in tannic acid equivalents before and after treatment, assayed the amount of protein precipitated phenolics. The results of all assays allowed differentiation between monophenolics (Gibbs), polyphenolics (Prussian Blue), total phenolics (Folin-Ciocalteau), complexation of added phenol and protein-precipitated phenolics. The reaction mechanisms underlying the assays were matched onto those occurring during humification. The assays were applied to six filtered freshwater samples and two humic and two fulvic acids. The results showed a different pattern for each site and illustrated varying reactivity of the 'phenolic content' of freshwater.     

官厅水库入库断面水质多指标评价与演变特征分析

水体质量状况及其污染特征是流域水污染防治规划和治理措施制定的前提和基础。采用主成分分析和层次聚类分析等多元统计分析方法,选取溶解氧、高锰酸盐指数、化学需氧量等10个不同类型的监测指标,综合评价了官厅水库入库断面八号桥2006—2017年丰水期和枯水期水质年际变化特征,识别了不同阶段关键污染指标。结果表明:各年份丰水期(9月)大多数水质指标均优于枯水期(5月),特别是粪大肠菌群和氨氮,但总磷和高锰酸盐指数的差异较小。根据水质指标年际变化情况,可将研究期分为污染严重阶段(2006—2007年)、污染改善阶段(2008—2015年)和污染全面好转阶段(2016—2017年)。大部分水质指标呈现逐年好转的趋势,特别是粪大肠菌群、氨氮和五日生化需氧量,但总磷仍是官厅水库入库河流的重要污染指标。     

Fluorescent screening of phytoplankton and organic compounds in sea water

The flow-through spectrofluorometers, FLUO-IMAGER, were developed to measure the abundance of phytoplankton, including the analysis of pigment composition and concentration of organic pollution and dissolved organic matter (DOM), in continuous mode. The measurements can be carried out without the time-consuming pretreatment of water samples. The analytical concept uses the technique of spectral fluorescent signatures (SFS), based on the systematized spectral library comprising the SFS of major phytoplankton species and chemical pollution. The SFS technique has been applied for several years in qualitative and quantitative screening of organic compounds and phytoplankton in the Baltic, North and Norwegian Seas. The results of the analysis of phytoplankton pigments, the dynamic processes of bloom development, DOM and oil pollution are presented.     

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.     

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.     

Water quality assessment of Ogun river, South West Nigeria

The quality of Ogun river in South-West, Nigeria was studied by a field survey for a period of 1 year (covering dry season and rainy season). Water samples were collected from thirteen sites and analysed for physico-chemical and bacteriological parameters as well as heavy metals using standard methods. Generally, the values obtained for turbidity, phosphate, oil and grease, iron and faecal coliform from all the sites in both seasons were above the maximum acceptable limit set by the World Health Organization (WHO) for drinking water. Also, the manganese content from all the sites in the dry season, lead concentrations from three sites in the dry season and cadmium concentrations from some sites in both seasons were above the WHO limit. The values obtained for total dissolved solids, dissolved oxygen and chloride at site M in the dry season and nitrate at site J in the rainy season were also above the WHO limit. Pollution of Ogun river water along its course is evidenced by the high concentrations of pollution indicators, nutrients and trace metals above the acceptable limit. This poses a health risk to several rural communities who rely on the river primarily as their source of domestic water. The study showed a need for continuous pollution monitoring programme of surface waters in Nigeria.     

Chemical and biological characteristics of streams in the Owabi watershed

In this investigation, concentrations of physico-chemical and bacteriological qualities of water samples from the major streams within the Owabi watershed in Kumasi, Ghana, were measured at five different locations. The streams were moderately soft and neutral, having a mean pH range of 7.08 ± 0.2 to 7.88 ± 0.6. Total dissolved solids, total suspended solids, grease and oil, alkalinity, and the major ion levels varied significantly at each sampling site. Nutrient levels were however low and did not show any clear variation at sample locations. The bacteriological quality of the water was poor, rendering it unsafe for domestic purposes without treatment. The poor bacteriological quality was due to direct contamination by animal and human wastes. The streams have an appreciable self-purification capacity which is stressed by persistent pollution overloads caused by expanding human activities within the catchment. Cluster analysis performed on the data to determine pollution patterns between the streams depicts that River Owabi was less polluted, Rivers Akyeampomene and Sukobri were moderately polluted, while River Pumpunase was highly polluted.     

Biogeochemical patterns in a river network along a land use gradient

The Bode catchment (Germany) shows strong land use gradients from forested parts of the National Park (23 % of total land cover) to agricultural (70 %) and urbanised areas (7 %). It is part of the Terrestrial Environmental Observatories of the German Helmholtz association. We performed a biogeochemical analysis of the entire river network. Surface water was sampled at 21 headwaters and at ten downstream sites, before (in early spring) and during the growing season (in late summer). Many parameters showed lower concentrations in headwaters than in downstream reaches, among them nutrients (ammonium, nitrate and phosphorus), dissolved copper and seston dry mass. Nitrate and phosphorus concentrations were positively related to the proportion of agricultural area within the catchment. Punctual anthropogenic loads affected some parameters such as chloride and arsenic. Chlorophyll a concentration and total phosphorus in surface waters were positively related. The concentration of dissolved organic carbon (DOC) was higher in summer than in spring, whereas the molecular size of DOC was lower in summer. The specific UV absorption at 254 nm, indicating the content of humic substances, was higher in headwaters than in downstream reaches and was positively related to the proportion of forest within the catchment. CO₂ oversaturation of the water was higher downstream compared with headwaters and was higher in summer than in spring. It was correlated negatively with oxygen saturation and positively with DOC concentration but negatively with DOC quality (molecular size and humic content). A principle component analysis clearly separated the effects of site (44 %) and season (15 %), demonstrating the strong effect of land use on biogeochemical parameters.     

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...     

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.     

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.     

Seasonal and spatial variation of reservoir water quality in the southwest of Ethiopia

This research investigated the spatiotemporal variation of water quality in the Gilgel Gibe reservoir, Ethiopia, using physicochemical water quality parameters. Nonparametric tests and multivariate statistical techniques were used to evaluate data sets measured during dry and rainy seasons. Electrical conductivity (EC), pH, biochemical oxygen demand (BOD₅), total phosphorus (TP), total nitrogen (TN), nitrate (NO₃^?), total dissolved solids (TDSs), and total suspended solids (TSSs) were all significantly different among seasons (Mann-Whitney U test, p?<?0.01). In addition, principal component analysis distinguished dry season samples from wet season samples. The dry season was positively associated with EC, pH, TP, TN, NO₃^?, TDS, and TSS and negatively associated with BOD₅. The wet season was in contrast associated with high values of turbidity, soluble reactive phosphorus (SRP), water temperature, and dissolved oxygen (DO). Within the reservoir, spatial variation was observed for some of the water quality parameters, with significant difference at p?=?<?0.05. Overall, high nutrient concentrations suggest eutrophic conditions, likely due to high nutrient loading from the watershed. Levels of TSS, attributed to inputs from tributaries, have been excessive enough to inhibit light penetration and thus have a considerable impact on the aquatic food web. Our findings indicate that the reservoir is at high risk of eutrophication and siltation, and hence, urgent action should target the planning and implementation of integrated watershed management for this and similar reservoirs in the region.     

Statistical analyses of coastal water quality for a port and harbour region in India

A long-term study of temperature, pH, turbidity, suspended solid, salinity, dissolved oxygen, biochemical oxygen demand and ammonia nitrogen has been performed in a port and harbour region in India for four years from December 1996 to November 2000. Marine water quality results showed no regular trend. The mean monthly values of temperature, pH, turbidity, suspended solid, salinity, dissolved oxygen, biochemical oxygen demand and ammonia nitrogen were in the range of 22.64 ± 0.4 to 29.05 ± 1.37 °C; 7.65 ± 0.04 to 7.81 ± 0.13; 28.8 ± 14.7 to 64.2 ± 32.0 NTU; 283.5 ± 81.8 to 356.0 ± 159.7 mg/L; 29.78 ± 7.18 to 29.78 ± 1.04 ppt; 4.67 ± 0.50 to 6.01 ± 1.02 mg/L; 5.41 ± 1.92 to 7.56 ± 2.1 mg/L; and 0.25 ± 0.07 to 0.63 ± 0.49 mg/L, respectively. The results of correlation analysis showed that biochemical oxygen demand (BOD) was inversely correlated dissolved oxygen (DO) and poorly correlated with all other parameters. Turbidity and suspended solid were moderately correlated with each other while salinity was moderately correlated with other water quality parameters. In factor analysis, four factors were drawn out of the eight variables, which represented 74% of the variance of the original data. Factor I was related to suspended solid and turbidity. Factor II represented mainly temperature and DO showing inverse relation between these two. Factor III implied the degree of pollution at any monitoring station. Factor IV included pH and salinity. It could be concluded that the factor model represented almost all the variables.     

Simulating Nitrate Leaching Profiles in a Highly Permeable Vadose Zone

An approach is developed to simulate leaching of a dissolved chemical constituent in the vadose zone of an aquifer. Specifically, nitrate loading at the water table for different water table depths, for a range of aquifer permeability values, and for different cases of heterogeneity of the aquifer, are considered. Models from the literature are first used to derive soil–water characteristic curves (water retention and hydraulic conductivity) from a grain size distribution curve for unsaturated conditions. Given infiltration from the surface, the initial conditions for the chemical concentration, and the water content profile, leaching of the chemical in the vadose zone is simulated as a function of both time and depth. The methodology is illustrated for a permeable aquifer. Simulations are undertaken using a finite element code for saturated and unsaturated flow. Different scenarios are simulated depending on the heterogeneity of the aquifer and the depth of the water table. Modeling results show that in the example case studied, nitrate concentration loading at the water table does not depend strongly on the position of the water table, but rather on the material properties of the aquifer. The contribution of this endeavor resides in the methodology which allows a prediction of nitrate leaching using only the grain size property of the aquifer. It allows practitioners to obtain a first assessment of leaching with limited data.     

Preliminary assessment of total dissolved trace metal concentrations in Sava River water

This study provides the preliminary data set for total dissolved trace metal concentrations in the surface water of the Sava River in Croatia and the assessment of Sava River water quality status. The highest levels of total dissolved metals were observed for Fe, Mn, and Zn (12.6 +/- 7.8 mirog L(-1), 3.44 +/- 3.95 mirog L(-1), and 2.27 +/- 1.53 mirog L(-1), respectively), the intermediate concentrations for Ni, Cu, and Cr (0.59 +/- 0.14 mirog L(-1), 0.54 +/- 0.14 mirog L(-1), and 0.32 +/- 0.06 mirog L(-1), respectively), and the lowest levels for Co, Pb, and Cd (0.064 +/- 0.022 mirog L(-1), 0.055 +/- 0.051 mirog L(-1), and 0.011 +/- 0.004 mirog L(-1), respectively). The results refer to the grab water samples taken at five sites in the period from March to June, 2006. For four trace metals (Mn, Pb, Zn, and Fe), the high temporal variability within one season was observed. It can present a problem for reliable evaluation of total dissolved concentrations of these metals in the river water, if the assessment is based on the occasional grab water sampling. The comparison of results obtained in this study with previously reported data for several unpolluted rivers indicated that Sava River water reflects a certain anthropogenic impact. However, according to the levels proposed by European regulations, it still can be classified as water containing total dissolved trace metals in concentrations not significantly above the natural level.     

Multiscale Spatial and Small-Scale Temporal Variation in the Composition of Riverine Fish Communities

We studied the multiscale (sites, river reaches and rivers) and short-term temporal (monthly) variability in a freshwater fish assemblage. We found that small-scale spatial variation and short-term temporal variability significantly influenced fish community structure in the Macquarie and Namoi Rivers. However, larger scale spatial differences between rivers were the largest source of variation in the data. The interaction between temporal change and spatial variation in fish community structure, whilst statistically significant, was smaller than the variation between rivers. This suggests that although the fish communities within each river changed between sampling occasions, the underlying differences between rivers were maintained. In contrast, the strongest interaction between temporal and spatial effects occurred at the smallest spatial scale, at the level of individual sites. This means whilst the composition of the fish assemblage at a given site may fluctuate, the magnitude of these changes is unlikely to affect larger scale differences between reaches within rivers or between rivers. These results suggest that sampling at any time within a single season will be sufficient to show spatial differences that occur over large spatial scales, such as comparisons between rivers or between biogeographical regions.     

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.