Spatial distribution of trace metals in the Krka River, Croatia: an example of the self-purification

The spatial distribution of dissolved and total trace metals (Zn, Cd, Pb and Cu) in the Krka River (partly located in the Krka National Park) has been studied using a "clean" sampling, handling and analysis technique. Differential pulse anodic stripping voltammetry (DPASV) with a hanging mercury drop electrode (HMDE) has been used for trace metal analysis. The Krka River has been divided into the upper and lower flow region with respect to the metals concentration and main physico-chemical parameters. A significant increase in trace metal concentration as the result of the untreated waste water discharge downstream of Knin Town has been registered in the upper flow region. Due to a specific characteristic of the Krka, the so-called self-purification process, a decrease in the elevated trace metals concentration from the water column takes place at numerous small lakes formed by tufa barriers (at the end of the upper flow region). The clean groundwater input at the beginning of the lower flow region additionally contributes to the observed decrease in trace metals concentration in the Krka, maintaining them at a very low level in the remaining region of fresh-water flow. The determined median total concentrations were zinc 120-7400 ng l(-1), cadmium 3-8 ng l(-1), lead 11-250 ng l(-1) and copper 110-440 ng l(-1). Karst rivers, such as the Krka River, with extremely low natural concentrations of trace metals are highly sensitive to the anthropogenic influence. Therefore, such aquatic systems require implementation of strict protection regimes in the entire catchments area.     

Climate and land-use changes affecting river sediment and brown trout in alpine countries—a review

Background, aim, and scope

Catch decline of freshwater fish has been recorded in several countries. Among the possible causes, habitat change is discussed. This article focuses on potentially increased levels of fine sediments going to rivers and their effects on gravel-spawning brown trout. Indications of increased erosion rates are evident from land-use change in agriculture, changes in forest management practices, and from climate change. The latter induces an increase in air and river water temperatures, reduction in permafrost, changes in snow dynamics and an increase in heavy rain events. As a result, an increase in river sediment is likely. Suspended sediment may affect fish health and behaviour directly. Furthermore, sediment loads may clog gravel beds impeding fish such as brown trout from spawning and reducing recruitment rates. To assess the potential impact on fine sediments, knowledge of brown trout reproductive needs and the effects of sediment on brown trout health were evaluated.

Approach

We critically reviewed the literature and included results from ongoing studies to answer the following questions, focusing on recent decades and rivers in alpine countries.

Have climate change and land-use change increased erosion and sediment loads in rivers?

Do we have indications of an increase in riverbed clogging?

Are there indications of direct or indirect effects on brown trout from increased suspended sediment concentrations in rivers or from an increase in riverbed clogging?

Results

Rising air temperatures have led to more intensive precipitation in winter months, earlier snow melt in spring, and rising snow lines and hence to increased erosion. Intensification of land use has supported erosion in lowland and pre-alpine areas in the second half of the twentieth century. In the Alps, however, reforestation of abandoned land at high altitudes might reduce the erosion risk while intensification on the lower, more easily accessible slopes increases erosion risk. Data from laboratory experiments show that suspended sediments affect the health and behaviour of fish when available in high amounts. Point measurements in large rivers indicate no common lethal threat and suspended sediment is rarely measured continuously in small rivers. However, effects on fish can be expected under environmentally relevant conditions. River bed clogging impairs the reproductive performance of gravel-spawning fish.

Discussion

Overall, higher erosion and increased levels of fine sediment going into rivers are expected in future. Additionally, sediment loads in rivers are suspected to have considerably impaired gravel bed structure and brown trout spawning is impeded. Timing of discharge is put forward and is now more likely to affect brown trout spawning than in previous decades.

Conclusions

Reports on riverbed clogging from changes in erosion and fine sediment deposition patterns, caused by climate change and land-use change are rare. This review identifies both a risk of increases in climate erosive forces and fine sediment loads in rivers of alpine countries. Increased river discharge and sediment loads in winter and early spring could be especially harmful for brown trout reproduction and development of young life stages. Recently published studies indicate a decline in trout reproduction from riverbed clogging in many rivers in lowlands and alpine regions. However, the multitude of factors in natural complex ecosystems makes it difficult to address a single causative factor.

Recommendations and perspectives

Further investigations into the consequences of climate change and land-use change on river systems are needed. Small rivers, of high importance for the recruitment of gravel-spawning fish, are often neglected. Studies on river bed clogging are rare and the few existing studies are not comparable. Thus, there is a strong need for the development of methods to assess sediment input and river bed clogging. As well, studies on the effects to fish from suspended sediments and consequences of gravel beds clogging under natural conditions are urgently needed.     

Health risks of environmental exposure to metals and herbicides in the Pardo River,Brazil

Mixture of metals and herbicides in rivers may pose relevant risks for the health of surrounding communities. Humans may be exposed to river pollution through intake of contaminated water and fish, as well as irrigated agricultural products. The aim of this study was to assess the human health risks of environmental exposure to metals and herbicides through water and fish intake in the Pardo River. Metals (Al, As, Be, Cd, Cr, Cu, Pb, Mn, Hg, Ni, Tl, Sn, V, and Zn) were analyzed in river water and in edible fish. Herbicides (ametryn, atrazine, diuron, hexazinone, simazine, and tebuthiuron) were analyzed in river water. Seasonal variances were also studied. Aluminum, Cd, Cu, Mn, Pb, and Zn levels in river water were higher than the USEPA benchmarks. Non-carcinogenic risks due to pollutants mixture exposure were above the limit, and carcinogenic risks of As exposure were >10^?6 in the sampling points during the rainy season. Metal levels in fish were lower than the Brazilian legislation and do not pose a threat to public health. Herbicides were detected in four sampling points, with atrazine concentrations (range 0.16–0.32 μg/L) below the Brazilian standard (2.0 μg/L), but above the European Union standard (0.1 μg/L). Considering the water supply needs of cities located in the Pardo River Basin and the persistence of metals and herbicides, the present study indicated that there was a seasonal influence on non-carcinogenic and carcinogenic risks to human health, especially in the rainy season. Studies for water treatment plants implantation should consider the risks of exposure to persistent substances, in order to protect the population.     

Assessment of heavy metal pollution in wetland soils from the young and old reclaimed regions in the Pearl River Estuary, South China

Soils were sampled in three types of wetlands from the young (A) and old (B) reclaimed regions of the Pearl River Estuary. They were analyzed for total concentrations of heavy metals to investigate their distributions and pollution levels in both regions. Results showed that most heavy metals in ditch and riparian wetlands did not significantly differ from those in reclaimed wetlands in A region, while significantly lower for Cd, Cu, Pb, and Zn in reclaimed wetlands in B region, suggesting higher effects of long-term reclamation. Iron, Cr and Cu were identified as metal pollutants of primary concern and had higher contributions to the total toxic units compared to other metals. Almost all metals exceeded their lowest effect levels and Fe and Cr even exceeded the severe effect levels. Multivariate analysis shows that Fe and Mn are controlled by parent rocks and other metals mainly originate from anthropogenic source.     

Heavy metal pollution in sediments of the Pasvik River drainage

The purpose of this paper is to study the regional impacts of heavy metals (Ni, Cu, Co, Zn, Cd, Pb, Hg) on the watershed of the Pasvik River. On the basis of sediment investigations at 27 stations of the watershed, background concentrations of the heavy metals, vertical distribution of heavy metals in sediments, heavy metal concentrations in surface sediments, contamination degree, and risk index were determined. The atmospheric emissions of Ni, Cu, Co, Zn, Cd and Hg from the smelters and waste waters from tailing dams and mines of the Pechenganickel Company are likely to be the main sources of increasing concentrations observed in recent sediments of the lower river reaches. Lead showed a different pattern from the other heavy metals--increasing Pb concentrations in the upper sediment layers towards the Norwegian side.     

Heavy metal (Cd, Cr, Cu, Hg, Pb, Zn) concentrations in seven fish species in relation to fish size and location along the Yangtze River

Purpose

The objective of this paper is to assess the regulation of the accumulation of heavy metals in the aquatic environment and different fish species.

Methods

Water and fish samples were collected from upper to lower reaches of the Yangtze River. The heavy metal (Cd, Cr, Cu, Hg, Pb, Zn) concentrations in the muscle tissue of seven fishes were measured. Additionally, the relationships between heavy metal concentrations in fish tissue and fish size (length and weight), condition factor, water layer distribution, and trophic level were investigated.

Results

Metal concentrations (milligrams per kilogram wet weight) were found to be distributed differently among different fish species. The highest concentrations of Cu (1.22?mg/kg) and Zn (7.55?mg/kg) were measured in Pelteobagrus fulvidraco, the highest concentrations of Cd (0.115?mg/kg) and Hg (0.0304?mg/kg) were measured in Silurus asotus, and the highest concentrations of Pb (0.811?mg/kg) and Cr (0.239?mg/kg) were measured in Carassius auratus and Cyprinus carpio. A positive relationship was found between fish size and metal level in most cases. The variance of the relationships may be the result of differences in habitat, swimming behavior, and metabolic activity. In this study, fishes living in the lower water layer and river bottom had higher metals concentrations than in upper and middle layers. Benthic carnivorous and euryphagous fish had higher metals concentrations than phytoplankton and herbivorous fish. Generally, fish caught from the lower reach had higher metals concentrations than those from the upper reach.

Conclusions

Cadmium and lead concentrations in several fishes exceeded the permissible food consumption limits, this should be considered to be an important warning signal.     

深圳市河流沉积物重金属污染特征及评价

分析了深圳市的深圳河、布吉河、龙岗河和茅洲河等4条河流沉积物中重金属的含量和富集状况,并对重金属污染的潜在生态危害进行了评价。结果表明：（1）1996-2003年,深圳河、布吉河、龙岗河和茅洲河沉积物中重金属的含量都有上升的趋势;布吉河和龙岗河沉积物中的重金属含量较高,特别是Cu、Zn和Cr的含量比其他两条河流高出较多,深圳河居中,茅洲河较小;这4条河流都以Cd、Cu、Cr和Zn的富集为主。（2）在研究时段内,这4条河流沉积物重金属污染的潜在生态危害指数（RI）都有上升的趋势;其中深圳河,布吉河和龙岗河的RI在多数年份都达到强或很强的程度,Cd、Hg、Cu为主要贡献元素;4条河流中,茅洲河受重金属污染最小,其RI为轻微或中等,只有Cd和Hg的生态危害系数为中等或强。针对深圳市河流沉积物中重金属的累积机理,建议通过改善区域水文条件、控制污染物的排放等措施加以控制和治理。     

Trace metals in flounder, Platichthys flesus (Linnaeus, 1758), and sediments from the Baltic Sea and the Portuguese Atlantic coast

Trace metals were examined in the muscle tissue of flatfish species of flounder, Platichthys flesus (Linnaeus, 1758), sediments from two southern Baltic Sea sites (Gdańsk Bay and Ustecko-?ebskie as a reference) and in two areas of the Portuguese Atlantic coast (Douro River estuary and Atlantic fishing ground as a reference) to evaluate spatial differences in trace metals. Additionally, the accumulation of trace metals in flounder of different length classes was assessed. Flounder from the Gdańsk Bay area contained twofold more cupper (Cu), lead (Pb) and mercury (Hg) than did flounder from the Douro River estuary, but zinc (Zn) and cadmium (Cd) were at similar concentrations. The sediments from Gdańsk Bay contained significantly more Zn and threefold more Cd, while concentrations of Cu and Pb were twofold lower. The concentrations of metals in the sediments did not correlate with those in the flounder. Spatial differences were noted in metal concentrations in flounder from the southern Baltic Sea and the Portuguese Atlantic coast as well as within these regions, with higher concentrations in the flounder from the Baltic Sea Gdańsk Bay. The flounder in length class 25–30 cm from Gdańsk Bay contained metal concentrations comparable to those of class 40–45 cm specimens from the Atlantic coast. The accumulation of metals in flounder length classes differed in the two regions.     

A 59-year sedimentary record of metal pollution in the sediment core from the Huaihe River,Huainan, Anhui,China

An approximately 59-year (1955–2014) sedimentary record of metal elements (Cu, Pb, Zn, Ni, Co, Mn, and Fe) in a sediment core, collected from the Huaihe River, Huainan City, Anhui Province, China, was reconstructed by using ²¹⁰Pb geochronology. Copper, Zn, Ni, Co, and Mn evaluated by enrichment factor (EF) indicated minor contamination due to water pollution accidents of the Huaihe River that occurred in 1990s and 2004. Lead presented the most severe pollution among the metals studied, especially during 1957–1974. The use of leaded petrol and atmospheric deposition of coal combustion flue gases could have contributed to Pb contamination. In spite of the general good quality (mean sediment pollution index (SPI) 35.69) of the sediment core evaluated by SPI based on the principal component analysis, worse sediment qualities in the upper section (<6 cm, 2004) were still observed, suggesting intensive human activities causing the increasing concentrations of metals in recent decades.     

Health risk assessment of heavy metals in Cyprinus carpio (Cyprinidae) from the upper Mekong River

The purposes of this research are to quantify the concentration of heavy metals (Zn, Cu, As, Pb, Cd, and Hg) in the water and fish tissues of common carp (Cyprinus carpio) in the upper Mekong River and to thereby elucidate the potential dietary health risks from fish consumption of local residents. Surface water and fish tissues (gill, muscle, liver, and intestine) from four representative sample areas (influence by a cascade of four dams) along the river were analyzed for heavy metal concentrations. Results revealed that the levels of heavy metals in fish were tissue-dependent. The highest Cu and As levels were found in the liver; the highest Zn and Pb levels occurred in the intestine, and the highest Hg level was found in the muscle. The total target hazard quotient (THQ) value for residents is > 1 for long-term fish consumption, and local residents are, therefore, exposed to a significant health risk. Results from the current study provide an overall understanding of the spatial and tissue distribution of heavy metals in water and fish body along the upper Mekong River under the influence of cascade dams and highlight the potential health risk of As for the local residents of long-term fish consumption.

     

Mercury (Hg) in fish consumed by the local population of the Jaguaribe River lower basin,Northeast Brazil

The knowledge of Hg concentrations in fish is of considerable interest since these organisms are a major source of protein to coastal human populations and fishing communities. The main source of human exposure to Hg contamination occurs through the consumption of fish. In this paper, we compare Hg concentration in 13 fish species from Jaguaribe River lower basin and an adjacent coastal region in the northeastern coast of Brazil. We sampled fish from three stretches of the river: fluvial, estuarine, and marine regions. We tested the hypothesis that Hg concentration in muscle tissue vary according to species, location, and trophic level. Significant differences were observed among species and trophic level, but these could not be observed among the regions studied. As expected, the highest concentrations were observed in carnivorous fish (5.6–107.5; 26.9?±?18.8 ng g^?1). Hg concentrations observed in this study are similar to those observed in regions of low environmental contamination. We estimated Hg intake to vary between 0.02 and 0.22 ng Hg kg body weight^?1 week^?1, for the average body weight of 56.7 kg, which was considered as low exposure and therefore, a low risk to consumers of fish from the regions studied.     

Genetic population structure of fishes: implications for coastal zone management

The pattern for distribution of genetic variation within and between populations is referred to as the genetic population structure of the species. To avoid depletion of genetic resources sustainable management should be based on knowledge of this structure. We discuss key aspects of genetic population structure in the context of identifying biological units for fisheries management, suggesting three basic types of structuring: distinct populations; continuous change; and no differentiation. The type of structure determines how units for genetically sustainable management are to be identified. We also review what is currently known regarding the genetic population structure of fishes exploited in the Swedish part of the Baltic Sea, and conclude that sufficient genetic information is lacking for most of the species. This is a serious problem, particularly considering that populations of several commercially exploited fishes are declining and some exhibit recruitment problems. For six species, Atlantic herring, Atlantic salmon, brown trout, European eel, turbot, and pike, sufficient genetic data are available to provide at least basic information on genetic structure and genetic units for biologically sustainable use. Current management practices do not sufficiently consider these data.     

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin,Southwestern India

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary–Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.     

Challenges with tracing the fate and speciation of mine-derived metals in turbid river systems: implications for bioavailability

The fast-flowing and highly turbid Lagaip River (0.5–10 g/L suspended solids) in the central highlands of Papua New Guinea receives mine-derived metal inputs in both dissolved and particulate forms. Nearest the mine, metal concentrations in suspended solids were 360, 9, 90, 740 and 1,300 mg/kg for As, Cd, Cu, Pb and Zn, while dissolved concentrations were 2.7, 0.6, 3.1, 0.1 and 25 μg/L, respectively. This creates a significant metal exposure source for organisms nearer the mine. However, because the Lagaip River is diluted by a large number of tributaries, the extent to which mine-derived metals may affect biota in the lower catchments is uncertain. To improve our understanding of the forms of potentially bioavailable metals entering the lower river system, we studied the partitioning and speciation of metals within the Lagaip River system. Dissolved and particulate metal concentrations decreased rapidly downstream of the mine due to dilution from tributaries. As a portion of the particulate metal concentrations, the more labile dilute acid-extractable forms typically comprised 10–30 % for As and Pb, 50–75 % for Cu and Zn, and 50–100 % for Cd. Only dissolved Cd, Cu and Zn remained elevated relative to the non-mine-impacted tributaries (<0.03, 0.5 and 0.3 μg/L), but the concentrations did not appreciably change with increasing dilution downriver. This indicated that release of Cd, Cu and Zn was likely occurring from the more labile metal phases of the mine-derived particulates. Chelex-labile metal analyses and speciation modelling indicated that dissolved copper and lead were largely non-labile and likely complexed by naturally occurring organic ligands, while dissolved cadmium and zinc were predominantly present in labile forms. The study confirmed that mine-derived particulates may represent a significant source of dissolved metals in the lower river system; however, comparison with water quality guidelines indicates the low concentrations would not adversely affect aquatic life.     

Liming of River Audna,Southern Norway: a large-scale experiment of benthic invertebrate recovery

This study describes the recovery of sensitive invertebrates after liming of the anadromous part of River Audna in 1985. The river lost its salmon population during 1960-1970. The aim of the liming was to produce a water quality with pH > 6.0 and ANC > 20 microg L(-1) and to reduce the content of labile aluminum. Highly sensitive invertebrates like the mayfly Baetis rhodani were not found in the river before liming. Two years after liming, several sensitive invertebrate species showed a positive response. B. rhodani was then recorded at 2 sites in the lower part of the river. In the following 5 years several species of sensitive invertebrates recolonized the whole limed reach of the river and became numerous. Ten years after liming the snail Lymnaea peregra was recorded in the river. The dispersa of this species was also very fast and after 5 years it was found at all investigated sites in the limed main river covering a reach of 40 km. Reduced sulfur deposition in the area also resulted in water-quality improvements in th unlimed stretches of River Audna. Comparisons between limed and unlimed localities indicated that the water quality and the critical limits of sensitive species are the ma factors determining the fauna composition in River Audna independent of the reason for the change in water quality.     

Use of blood parameters in fish to assess acidic stress and chloride pollution in French running waters

The study investigated whether plasmatic parameters in fish such as Cl- content could serve as physiological indicators to evaluate water quality. The variations of plasma Cl- content in two fish species caught in a wide range of rivers representative of the hydrographic system of Lorraine (N-E France) were investigated. First, we studied autochthonous populations of chub (Leuciscus cephalus) which is a widespread species in the rivers of Lorraine. Organisms living in highly mineralised rivers (>1500 microScm(-1))--either naturally or due to salt mine contamination--showed plasma Cl- content significantly greater than organisms living in river with a lower mineralisation. Second, we investigated plasma Cl- content of brown trout (Salmo trutta fario) in poorly mineralised streams (<80 microS cm(-1)) with different degrees of acidification, both on autochthonous and transferred organisms. While indigenous trout maintained their Cl- content even in the acidic streams, transferred trout exhibited an important decrease of Cl- content after 48 h of exposure under acidic conditions.     

Concentrations,spatial distribution,and pollution assessment of heavy metals in surficial sediments from upstream of Yellow River,China

Surface sediments were collected from 122 sites in the upstream of the Yellow River, China. The concentration of Fe, Mn, Cu, Ni, Zn, Cr, Pb, and Cd in sediments was investigated to explore the spatial distribution based on statistics and interpolation method. The results suggested that the concentrations of heavy metals were lower than potential effect levels (PEL). The samples above threshold effect level (TEL) for Pb and Zn were less than 10%, while almost 50% of samples for Ni exceeded PEL. Pb and Zn in sediments performed little or no adverse effects on the aquatic ecosystems. Higher concentrations of all heavy metals occurred in Qinghai and Gansu sections; the concentrations of Cu, Ni, and Zn were significantly higher than the Inner Mongolia section. Lower concentration of Fe, Mn, Cu, Ni, and Zn appeared in Qinghai section; the concentrations of Fe, Mn, Cr, and Pb manifested relatively steady and similar distributions and approximately decreasing tendency along the upstream of Yellow River.

     

Distribution and fractionation of heavy metals in the Tisa (Tisza) River sediments

Introduction In this work, sediments of the River Tisa (Tisza) are studied to assess their environmental pollution levels for some major heavy metals, as well as to predict the investigated elements’ mobility on the basis of their association type with the substrate. The Tisa River catchments area is a subbasin of the River Danube. Part of this river, 166 km long, belongs to the Serbian province of Vojvodina, before it flows into the Danube. It has been chosen for our investigation, because it has been exposed to intense pollution in the last decades. Materials and Methods The river sediment samples were collected at 32 locations. The proportions of sand, silt and clay fractions were determined. The sequential extraction procedure following a modified Tessier method was applied for speciation of the metal forms in the collected samples. The metal concentrations of Zn, Cd, Pb, Ni, Cu, Cr, Fe and Mn in extracts were determined by atomic absorption spectroscopy. Results and Discussion Granulometric analysis showed that some 50% of the Tisa River sediments were silt and clay, while the rest was sand with quartz, as the main constituent. The average metal content of the surface river sediment samples for every fraction of sequential extraction was presented and discussed in relation to pH, Eh and metal fractionation. The average metal content from the Tisa River sediments, obtained as an average of the metal’s concentration released in all five sequential extraction fractions was compared with: average metal contents of the Tisa River sediments in Hungary, metal content in soils formed on the Tisa River alluvium of Vojvodina, average metal content in soils of Vojvodina, and average metal content in soils of Hungary. An assessment of metal pollution levels in Tisa River sediments was made by comparing mean values for obtained results for the Tisa River sediments with the freshwater sediment’s Quality Guidelines as published by US EPA, Environment Canada and soil standards for Serbia. Conclusion According to US EPA and Canadian Quality Guidelines for freshwater sediments, the concentration of heavy metals in Tisa sediments were: (a) much higher than defined concentrations below which harmful effects on river biota are unlikely to be observed, (b) below defined concentrations above which harmful effects on river biota are likely to be observed. The concentration levels of Pb, Ni, Cu and Cr in Tisa River sediments are safe when compared with Serbian MAQ (Maximum Allowed Quantity) standards for soils, but they are unsafe in the case of Zn and Cd. Recommendations and Outlook The quality of sediments in the Tisa River was on the border line between potentially polluted and polluted. This line could very easily be exceeded since the quality of sediments in the Tisa River in Hungary was already worse than in Serbia. These results indicated the need for further monitoring of heavy metals in that locality.     

Structural and optical characterization of dissolved organic matter from the lower Athabasca River, Canada

Dissolved organic matter (DOM) is a ubiquitous constituent of natural waters and is comprised of a variety of chemically heterogeneous molecular structures and functional groups. DOM is often considered to be a major ligand for metals in most natural waters and its reactivity is thought to be strongly dependent on its chemical composition and structure. In this study, a combination of UV/visible, emission excitation matrix fluorescence (EEM) and ¹H NMR spectroscopies were used to characterize DOM from the Athabasca River (Alberta, Canada). The chemical characterization of river DOM showed that the most upstream samples located in agricultural areas were blue-shifted and less aromatic and contained more hydrogens connected with oxygen functional groups than those in the wetland dominated area in the Athabasca oil sand deposit region. The presence of paramagnetic ions (Fe and Al) was not found to significantly affect the structural composition of DOM as revealed by ¹H NMR. Such change in the quality of DOM may have a profound impact on metal binding in the Athabasca River watershed.