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.     

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.     

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...     

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.     

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.     

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.     

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。     

Monitoring of heavy metal levels in roadside dusts of Thessaloniki, Greece in relation to motor vehicle traffic density and flow

In recent years, the level of heavy metal pollution in urban areas has been of considerable concern. The principal source has been attributed to the motor vehicle and increasing inner city congestion, which has lead to a change and enlargement of transport stop-start zones. These areas of high traffic density are associated with an increased release of heavy metals into the adjacent residential or commercial areas. Seventy-five roadside dust samples were collected throughout the inner city and by-pass motorway areas of Thessaloniki, Northern Greece. Samples were taken from arterial, major and minor roads, as well as the ring road, to compare and contrast the levels of heavy metals, namely Cu, Zn, Cd, Mn and Pb. Flame Atomic Absorption Spectroscopy (FAAS) was developed to quantitatively determine concentrations of both total element and geochemical fractionation, within the two dust particulate fraction sizes <75 microm and 75-125 microm. Acid digestion using Aqua Regia (3:1 conc. HCl:HNO(3)) was employed for the total elemental analysis, a method that was validated through the use of certified reference materials (CRM). Fractionation studies involved a three-step sequential extraction method performed on five selected samples (representatives of high, mid and low total elemental concentrations). The resultant solutions were analysed for lead and zinc levels to ascertain fractionation throughout the different geochemical fractions, thus assessing bioavailability.It was found that congestion/stop-start traffic patterns did influence and have led to increased levels of heavy metal deposition along inner city roads compared to levels observed on the new relief ring road. Dust particulate fraction sizes were only found to show statistically significant differences in cadmium and manganese, at the probability P < 0.001 or 99.9% confidence limit. Both Cd and Mn showed higher total levels in the smaller fraction sizes (<75 microm), implying that their major release source is exhaust emissions. There were no significant differences in the other elements, at the P > 0.05 or 95% confidence limit. Road type was seen to have little affect on cadmium and manganese, though lead, copper and zinc were all found to show higher levels on the inner city routes. This can be related back to the wear-and-tear of vehicle components as a result of the stop-start traffic patterns (brake pads etc). Both Pb and Zn have shown to be in chemical forms that are bio available to ecosystems.     

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.     

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.     

Fractionation and ecological risk of metals in urban river sediments in Zhongshan City, Pearl River Delta

Surface sediments collected from nine urban rivers located in Zhongshan City, Pearl River Delta, were analyzed for total concentration of metals with digestion and chemical fractionation adopting the modified European Community Bureau of Reference (BCR) sequential extraction procedure. The results showed that concentration and fractionation of metals varied significantly among the rivers. The total concentration of eight metals in most rivers did not exceed the China Environmental Quality Standard for Soil, Grade III. The potential ecological risk of metals to rivers were related to the land use patterns, in the order of manufacturing areas > residential areas > agriculture areas. The concentration of Pb in the reducible fraction was relatively high (60.0-84.3%). The dominant proportions of Cd, Zn and Cu were primary in the non-residual fraction (67.0%, 71.8% and 81.4% on average respectively), while the percentages of the residual fractions of Cr and Ni varied over a wide range (43-85% and 24-71% respectively). The approaches of the H?kanson ecological risk index and Secondary Phase Enrichment Factor were applied for ecological risk assessment and metal enrichment calculation. The results indicated Hg and Cd had posed high potential ecological risk to urban rivers in this region. Meanwhile, there was widespread pollution and high enrichment of Cu in river sediments in this region. Multiple regression analysis showed that five water quality parameters (pH, DO, COD(Mn), NH(4)(+)-N, TP) had little influence on the distribution of metal fractionation. This result revealed that the ecological risk of metals was not eliminated along with the improvement in water quality. Correlation studies showed that among the metals, Group A (Cd, As, Pb, Zn Hg, r = 0.730-0.924) and Group B (Cr, Cu, Ni, r = 0.815-0.948) were obtained, and the metal contaminations were from industrial activities rather than residential.     

Aquatic humus from an unpolluted Brazilian dark-brown stream: general characterization and size fractionation of bound heavy metals

The main pool of dissolved organic carbon in tropical aquatic environments, notably in dark-coloured streams, is concentrated in humic substances (HS). Aquatic HS are large organic molecules formed by micro-biotic degradation of biopolymers and polymerization of smaller organic molecules. From an environmental point of view, the study of metal humic interactions is often aimed at predicting the effect of aquatic HS on the bioavailability of heavy metal ions in the environment. In the present work the aquatic humic substances (HS) isolated from a dark-brown stream (located in an environmental protection area near Cubat?o city in S?o Paulo-State, Brazil) by means of the collector XAD-8 were investigated. FTIR studies showed that the carboxylic carbons are probably the most important binding sites for Hg(II) ions within humic molecules. 13C-NMR and 1H-NMR studies of aquatic HS showed the presence of constituents with a high degree of aromaticity (40% of carbons) and small substitution. A special five-stage tangential-flow ultrafiltration device (UF) was used for size fractionation of the aquatic HS under study and for their metal species in the molecular size range 1-100 kDa (six fractions). The fractionation patterns showed that metal traces remaining in aquatic HS after their XAD-8 isolation have different distributions. Generally, the major percentage of traces of Mn, Cd and Ni (determined by ICP-AES) was preferably complexed by molecules with relatively high molecular size. Cu was bound by fractions with low molecular size and Co showed no preferential binding site in the various humic fractions. Moreover, the species formed between aquatic HS and Hg(II), prepared by spiking (determined by CVAAS), appeared to be concentrated in the relatively high molecular size fraction F1 (> 100 kDa).     

流域重点工业污染源识别特征成分谱建立技术

研究了基于生产排放全过程、多相、多类污染物并举的污染源识别特征成分谱建立技术。首先建立污染源排放完整图谱,包括原辅料、中间物质、产品、各工艺废水污染物、水处理设施进口和出口污染物等。然后从排放完整图谱中解析出特征污染物。对于废水中的常规污染物和金属污染物,采用与受纳水体浓度相比较的方式得到污染源识别特征污染物,建议将浓度超过受纳水体1倍的污染物定为特征污染物。对于有机污染物,将质量分数之和大于90%的污染物集定为特征有机污染物,并按照有机物类别进行分类。最后开发建立动态的水污染源排放数据库。应用该技术建立了石化行业典型企业的排放特征成分谱,发现这些特征组分具有很好的代表性,为水污染源的识别提供了基础数据。     

Distribution and availability of trace elements in municipal solid waste composts

Trace element contamination is one of the main problems linked to the quality of compost, especially when it is produced from urban wastes, which can lead to high levels of some potentially toxic elements such as Cu, Pb or Zn. In this work, the distribution and bioavailability of five elements (Cu, Zn, Pb, Cr and Ni) were studied in five Spanish composts obtained from different feedstocks (municipal solid waste, garden trimmings, sewage sludge and mixed manure). The five composts showed high total concentrations of these elements, which in some cases limited their commercialization due to legal imperatives. First, a physical fractionation of the composts was performed, and the five elements were determined in each size fraction. Their availability was assessed by several methods of extraction (water, CaCl(2)-DTPA, the PBET extract, the TCLP extract, and sodium pyrophosphate), and their chemical distribution was assessed using the BCR sequential extraction procedure. The results showed that the finer fractions were enriched with the elements studied, and that Cu, Pb and Zn were the most potentially problematic ones, due to both their high total concentrations and availability. The partition into the BCR fractions was different for each element, but the differences between composts were scarce. Pb was evenly distributed among the four fractions defined in the BCR (soluble, oxidizable, reducible and residual); Cu was mainly found in the oxidizable fraction, linked to organic matter, and Zn was mainly associated to the reducible fraction (iron oxides), while Ni and Cr were mainly present almost exclusively in the residual fraction. It was not possible to establish a univocal relation between trace elements availability and their BCR fractionation. Given the differences existing for the availability and distribution of these elements, which not always were related to their total concentrations, we think that legal limits should consider availability, in order to achieve a more realistic assessment of the risks linked to compost use.     

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.     

Environmental study of two significant solid samples: gravitation dust sediment and soil

In this work are presented results of the complex study of two significant solid environmental samples: gravitation dust sediments (industrial pollutants, potential source of risk elements input to soils) and soils (component of the environment, potential source of risk elements input to food web). The first phase of this study was focused on the study of the significant chemical properties (phase composition, content of organic and inorganic carbon) of the dust and soil samples. In the second phase, the fractionation analysis was used on the evaluation of the mobility of chosen risk elements (Cu, Ni, Pb, Zn) in the studied samples. The single-step extractions were applied in the order of the isolation of the element forms (fractions), with different mobilities during defined ecological conditions by utilization of the following reagents: 1 mol dm^− 3 NH₄NO₃ for isolation of the “mobile” fraction, 0.05 mol dm^− 3 ethylenediaminetetraacetic acid and 0.43 mol dm^− 3 CH₃COOH for isolation of the “mobilizable” fraction, and 2 mol dm^− 3 HNO₃ for isolation of all releasable forms. On the basis of the results obtained in this study, it is possible to state that different origins and positions of solid environmental samples in the environment reflect in different chemical properties of their matrix. The different properties of the sample matrix result in different mobilities of risk elements in these kinds of samples. The fractionation analysis with single-step extraction for isolation element fractions is the method most suitable for easy checking of environmental pollution and for evaluation of risk elements cycle in the environment.     

Integrated pollution evaluation of the Tagus River in Central Spain

The aim of this study was to integrate hydrochemical and sediment data in order to obtain a picture of the pollution state of the Tagus River along central Spain. This area is of special interest because tributaries from the Madrid region are discharged and no previous data were available. Waters and sediments were sampled between 2002 and 2004 from selected sites before and after Jarama River confluence (Madrid city input). The samples were analysed for more than 50 parameters, including those of physico-chemical nature and those reporting the pollution caused by both metals and organic compounds. The quality of waters for different uses has been tested and statistical quality indexes of both global and partial type has also been established. Sediments pollution state was evaluated by comparison with general quality standards. A high degree of pollution and general degradation was observed in the Tagus River downstream the Jarama River input. The pollution of waters is mainly related to parameters indicators of organic pollution from urban sewage. In sediments, a dramatic increase in the concentration of trace metals was found in different points, exceeding toxicological threshold. Further studies would be necessary for organic pollutants and also to evaluate the remobilization potential.     

Identification of copper sources in urban surface waters using the principal component analysis based on aquatic parameters

The goal of this work was to identify the sources of copper loads in surface urban waters using principal component analysis under the aquatic parameters data evaluation approach. Water samples from the Irai and Iguacu rivers were collected monthly during a 12-month period at two points located upstream and downstream of a metropolitan region. pH, total alkalinity, dissolved chloride, total suspended solids, dissolved organic matter, total recoverable copper, temperature, and precipitation data provided some reliable information concerning the characteristics and water quality of both rivers. Principal component analysis indicated seasonal and spatial effects on copper concentration and loads in both environments. During the rainy season, non-point sources such as urban run-off are believed to be the major source of copper in both cases. In contrast, during the lower precipitation period, the discharge of raw sewage seems to be the primary source of copper to the Iguacu River, which also exhibited higher total metal concentrations.     

Chemical speciation and partitioning of trace metals (Cd, Co, Cu, Ni, Pb) in the lower Athabasca river and its tributaries (Alberta, Canada)

Concentrations of Cd, Co, Cu, Ni and Pb were measured in particulate and dissolved phases at 11 sites located upstream and near Athabasca oil sands development. The in situ discrimination between non-labile and labile dissolved metals was done using diffusive gradients in thin-films (DGT) devices. The DGT-labile fraction of Co and Ni was 30% lower near development sites whereas Cu, Cd and Pb showed minor changes spatially. It was found that an 8-fold increase in dissolved organic matter (DOM) near development induced a rapid decrease in DGT-labile metals. Dissolved metal concentrations were used along with DOM, major ions, nutrients, pH and conductivity to calculate the distribution of dissolved metal species using the speciation model WHAM. Labile-DGT metal concentrations agreed well with WHAM-predicted concentrations. It was also found that a significant amount of metals were associated with the non-DGT labile fraction (i.e. colloidal DOM) and colloid abundance was more important than suspended particulate matter abundance in influencing metal mobility near Athabasca oil soils development. Since changes in colloidal DOM levels are likely to be the result of surface mining activities, this confirms the serious effects of oil sands activities on metal biogeochemical cycles in the lower Athabasca River.