Factors controlling the accumulation of metals within fluvial systems

The magnitude and distribution of European Community (EC) regulated List I and List II metals and metalloids have been investigated in two lowland river systems in East Anglia, U.K. A combination of sediment and water quality data identified municipal sewage treatment work discharges as the main metal input sources to the river systems and identified two main areas of metal contamination: the Pix Brook, downstream of Letchworth STW on the River Ivel, and a 14 km enrichment zone adjacent to Whitlingham STW on the River Yare. The basement geology, flow dynamics, distance from point sources and sediment type were identified as important controls upon the magnitude and spatial distribution of metal contaminants.     

Multi-residues analysis of pre-emergence herbicides in fluvial sediments: application to the mid-Garonne River

Contamination of man and ecosystems by pesticides has become a major environmental concern. Whereas many studies exist on contamination from agriculture, the effects of urban sources are usually omitted. Fluvial sediment is a complex matrix of pollutants but little is known of its recent herbicide content. This study proposes a method for a fast and reliable analysis of herbicides by employing the accelerated solvent extractor (ASE). The aim of the study is to show the impact of a major town (Toulouse) on the herbicide content in the river. In this study, three herbicide families (i.e.s-triazine, substituted ureas and anilides) were analysed in fluvial sediment fractions at 11 sampling sites along the mid-Garonne River and its tributaries. River water contamination by herbicides is minor, except for at three sites located in urban areas. Among the herbicidal families studied, urban and suburban areas are distinguished from rural areas and were found to be the most contaminated sites during the study period, a winter low-water event. The herbicide content of the coarse sediment fractions is about one third of that found in the fine fractions and usually ignored. The distribution of pesticide concentrations across the whole range of particle sizes was investigated to clarify the role of plant remains on the significant accumulation in the coarse fractions.     

Traceability from weathered oil spills in the marine environment to the original contamination source. A case study

An algorithm for stepwise approximation to the most reliable source of contamination is proposed. The concept of the algorithm is based on discrimination rather than on similarity. Gradually, by means of more complicated and higher distinguishing power approaches, the differences between the spilled sample and the suspected source are checked. Capillary gas chromatography with flame-ionization and mass spectrometric detection was applied to gather the necessary data. Fingerprint, diagnostic parameter approaches and pattern recognition methods were used for reliably distinguishing the analytical results. If the compared samples are not discriminated by any means, they are considered as identical.     

The contribution of roadside soil to phosphorus loading in the eutrophic Lagos Lagoon, Nigeria

Roadside soils were sampled from the Lagos Lagoon catchment during the wet and dry seasons over the period 2005-2009. Lagoon sediment samples were also collected within the same period. All samples were digested with aqua regia to determine total phosphorus and extracted with 0.5 M sodium bicarbonate to determine the bioavailable fraction (Olsen-P). A segmented flow analyser method was used for analysis and good accuracy was demonstrated for two reference soils (SO-2 from CCMET and SRM 2711 from NIST). The Lagos Lagoon is a hypereutrophic water body (1270 ± 1170 μg P L(-1)), with significant areas of anoxia and water hyacinth growth. The total phosphorus concentrations in roadside soils (16 sites; mean ± 2 S.D.) were 285 ± 279 mg kg(-1) in the wet season and 424 ± 629 mg kg(-1) in the dry season, indicating that rainwater leaching is a major source of phosphorus in the lagoon. The bioavailable fractions were 5.17 ± 3.47 mg kg(-1) (2.1 ± 1.5% of the total) in the wet season and 13.0 ± 8.7 mg kg(-1) (4.3 ± 4.5% of the total) in the dry season.     

Analytical approaches to the determination of phosphorus partitioning patterns in sediments

Three methods for phosphorus fractionation in sediments based on chemical extractions have been applied to fourteen aquatic sediment samples of different origin and characteristics. Two of the methods used different approaches to obtain the inorganic fractions. The Hieltjes and Lijklema procedure (HL) uses strong acids or bases, whereas the Golterman procedure (G) uses chelating reagents. The third one, the Standards, Measurements and Testing (SMT) protocol, was proposed in the frame of the SMT Programme (European Commission) which aimed to provide harmonisation and the validation of such methodologies. This harmonised procedure was also used for the certification of the extractable phosphorus contents in a sediment certified reference material (CRM BCR 684). Principal component analysis (PCA) was used to group sediments according to their composition and the three extraction methods were applied to the samples including CRM BCR 684. The data obtained show that there is some correlation between the results from the three methods when considering the organic and the residual fractions together. The SMT and the HL methods are the most comparable, whereas the G method, using a different type of reagent, yields different distribution patterns depending on sample composition. In relation to the inorganic phosphorus, the three methods give similar information, although the distribution between non-apatite and apatite fractions can be different.     

A multi criteria analog model for assessing the vulnerability of rural catchments to road spills of hazardous substances

Road spills of hazardous substances are common in developing countries due to increasing industrialization and traffic accidents, and represent a serious threat to soils and water in catchments. There is abundant literature on equations describing the wash-off of pollutants from roads during a storm event and there are a number of watershed models incorporating those equations in storm water quality algorithms that route runoff and pollution yields through a drainage system towards the catchment outlet. However, methods describing catchment vulnerability to contamination by road spills based solely on biophysical parameters are scarce. These methods could be particularly attractive to managers because they can operate with a limited amount of easily collectable data, while still being able to provide important insights on the areas more prone to contamination within the studied watershed. The purpose of this paper was then to contribute with a new vulnerability model. To accomplish the goal, a selection of medium properties appearing in wash-off equations and routing algorithms were assembled and processed in a parametric framework based on multi criteria analysis to define the watershed vulnerability. However, parameters had to be adapted because wash-off equations and water quality models have been developed to operate primarily in the urban environment while the vulnerability model is meant to run in rural watersheds. The selected parameters were hillside slope, ground roughness (depending on land use), soil permeability (depending on soil type), distance to water courses and stream density. The vulnerability model is a spatially distributed algorithm that was prepared to run under the IDRISI Selva software, a GIS platform capable of handling spatial and alphanumeric data and execute the necessary terrain model, hydrographic and thematic analyses. For illustrative purposes, the vulnerability model was applied to the legally protected Environmental Protection Area (APA), located in the Uberaba region, state of Minas Gerais, Brazil. In this region, the risk of accidents causing chemical spills is preoccupying because large quantities of dangerous materials are transported in two important distribution highways while the APA is fundamental for the protection of water resources, the riverine ecosystems and remnants of native vegetation. In some tested scenarios, model results show 60% of vulnerable areas within the studied area. The most sensitive parameter to vulnerability is soil type. To prevent soils from contamination, specific measures were proposed involving minimization of land use conflicts that would presumably raise the soil's organic matter and in the sequel restore the soil's structural functions. Additionally, the present study proposed the preservation and reinforcement of riparian forests as one measure to protect the quality of surface water.     

The combined use of electrokinetic remediation and phytoremediation to decontaminate metal-polluted soils: a laboratory-scale feasibility study

The use of a combination of electrokinetic remediation and phytoremediation to decontaminate two metal-polluted soils has been demonstrated in laboratory-scale reactors. One soil was heavily contaminated with copper, the other with cadmium and arsenic (2500 g g^-1 Cu; 300-400 g g^-1 Cd and 230 g g^-1 As, respectively). Test reactors with twoseparated chambers, each with a capacity of 5.25 kg soil, wereconstructed, then the respective chambers were filled with eithera mixture of the polluted soil and a control topsoil (75:25) ortopsoil alone. Reactors were sown with perennial ryegrass (Lolium perenne cv Elka) and a constant voltage of 30 V was applied continually across the soils in each reactor. Soil sampling took place at the start and the end of the test run, whilst plant foliage was sampled after approximately 3 weeks (both reactors) 6 weeks (Cd soil reactor only) and at the conclusion of each test run (98 days Cu soil, 80 days Cd soil). Soil and plant metal concentrations were measured, together withsoil pH. Results showed that in both soils there was a significant re-distribution of metals from anode to cathode in the test reactors, coupled with an enhancement of plant Cu uptakein the cathode region for the Cu soil. Patterns of plant Cd uptake were less clear cut and were not as clearly related to theredistribution of Cd measured in the soil. There was significant acidification of soil at the anode in each test reactor, but soilpH in other parts of the reactor changed little during the courseof the experiment. Plant growth was affected at the anode, but was not affected in other parts of the reactor. There was no visual evidence of metal toxicity in the ryegrass in either polluted soil. Some effects on soil fungi were apparent, with a stimulation of Fusarium infection of ryegrass in the cathode region of all reactors and the appearance of sporophoresof Coprinus in the same location. It is concluded that the combination of the two techniques represents a very promising approach to the decontamination of metal polluted soils that nowrequires validation in field conditions.     

On the estimation of phosphorus from the Niagara River to Lake Ontario

A predictive or model based approach to making inferences about the loading of a contaminant from a point source is presented and illustrated by estimating the total phosphorus, TP, loading from the Niagara River to Lake Ontario for the years 1967 to 1982. Information about explanatory variables and/or autodependence among successive observations can be easily included in the model and this allows more accurate inferences to be made. The results of the application to the Niagara River show a major decrease in TP loadings has occurred during the study period.     

Phthalate and alkyl phenol concentrations in soil following applications of inorganic fertiliser or sewage sludge to pasture and potential rates of ingestion by grazing ruminants

Soil concentrations of dioctyl phthalate (DOP) and the alkyl phenols, octyl phenol (OP) and nonyl phenol (NP), after repeated surface applications of sewage sludge to pastures, were investigated. Liquid sludge was applied at a rate of 2.25 tonnes dry matter (DM) per hectare to each of three treated (T) plots on three occasions during the summer and two occasions in the early spring over a period of 2.5 years. Control (C) plots were treated with inorganic fertiliser containing amounts of nitrogen equivalent to those applied to the treated plots. At between 69 and 81 days after the application of sludge, 15 separate soil samples were collected from one half of each of the plots (Experiment 1). Concentrations (microg g(-1)) of DOP were higher (P < 0.001) than those of NP, while those of OP were generally below detectable levels. Mean soil concentrations of DOP were not significantly different in T and C plots [0.233 vs. 0.155 microg g(-1); standard error of the difference (SED) = 0.046; not significant (NS)], partly because there was already a relatively large amount of DOP present. NP concentrations were, however, significantly higher in T than in C plots (0.021 vs. 0.013 microg g(-1) SED = 0.002; P < 0.05). There was no consistent change over time in the mean soil concentrations of these compounds when sampled at intervals of 3-6 months. Concentrations in soil samples collected at monthly intervals following sludge application indicated that the variation in concentrations of these endocrine-disrupting compounds (EDC) was unrelated to time since sludge application. Rates of soil ingestion, expressed as the percentage of DM intake represented by soil, were higher during the winter than the summer (5.40 vs. 1.17; SED = 0.360; P < 0.001) and estimated daily intakes of DOP and NP were up to 150 microg and 8 microg, respectively. It is concluded that the application of sewage sludge to pasture does not increase soil concentrations of phthalate (as DOP) or alkyl phenols. Thus, the risk of increased exposure to these EDC as a result of sludge application is small. However, the small effect of sludge application on soil concentrations may be largely a reflection of the relatively high concentrations of DOP already present in the soil, which may be biologically significant.     

Water quality of selected fluvial lakes in the context of the Elbe River pollution and anthropogenic activities in the floodplain

The paper evaluates the status of selected fluvial lakes situated in the central part of the Elbe River and the impact of anthropogenic activities including comparison with the Elbe River water quality on them. To achieve the goals of the project, eight researched lakes differed from each other in the intensity of communication with the river, morphometric parameters and in the possibility of anthropogenic contamination (industrial, agricultural and municipal) were chosen. Besides observing the hydrological regime, the research was focused on physical and chemical parameters of water. To sum up, the lakes communicating above ground with the river showed similarities in several parameters, e.g. organic load or conductivity was nearly at the same level, which was lower than in the separated ones. Although the values of nitrates were higher in the river, their content did not reach such concentrations even in the connected lakes because of their more stagnant character. In general, although the Elbe River has a significant effect on water quality of researched lakes, especially in the case of lakes with a restricted communication with the river, their water quality is a result of local conditions, e.g. possibility of contamination by sewage waters, land use in the vicinity, etc.     

The effectiveness of composite lining systems in controlling the leakage of leachate from sanitary landfills to groundwater

Leachate, the hazardous liquid that percolated through the refuse layers of a sanitary landfill, if it leaks through the landfill lining system, can become a serious source of groundwater pollution. In the past, leaks have been detected in many landfills lined with flexible membrane liners (FML) whose failure may be attributed to flaws such as imperfect seaming, rips, and tears of the membrane, or from chemical attack that dissolves the membrane. Recent studies have shown that composite lining systems which include either a clayey subbase or a layer of geotextile in addition to the FML, can substantially reduce the leakage of leachate. Therefore in this study, four different lining systems are proposed and evaluated to determine their effectiveness in controlling leachate flow under various degree of flaws (referred to as leakage fraction LF) in the FML. The Hydrologic Evaluation of Landfill Performance (HELP) computer model of the Environmental Protection Agency of USA, currently the most widely accepted model for predicting the performance of leachate collection systems in that country, is used to evaluate the following lining systems: (1) a single FML or liner, (2) a single FML with a clayey composite, (3) a single FML with a geotextile called Claymax, and (4) a double FML. Based on the climatic conditions and the present lining construction cost of Alaska, the study shows that a single FML or liner is the most economical but it is also the least effective in controlling leachate flow. Design (3), a single FML with a geotextile, costs about 50 percent more but it reduces the leakage of leachate by several orders. Design (2) is also effective but the cost incurred in constructing a 3 feet thick clayey subbase is prohibitive and thus to effectively and economically minimize the hazards of potential groundwater contamination by leachate, Design (3) is recommended as the composite lining system for future landfill sites.     

Changes in labile soil organic matter fractions following land use change from monocropping to poplar-based agroforestry systems in a semiarid region of Northeast China

Labile fractions of soil organic matter (SOM) respond rapidly to land management practices and can be used as a sensitive indicator of changes in SOM. However, there is little information about the effect of agroforestry practices on labile SOM fractions in semiarid regions of China. In order to test the effects of land use change from monocropping to agroforestry systems on labile SOM fractions, we investigated soil microbial biomass C (MBC) and N, particulate organic matter C (POMC) and N (POMN), as well as total organic C (TOC) and total N (TN) in the 0- to 15-cm and the 15- to 30-cm layers in 4-year-old poplar-based agroforestry systems and adjoining monocropping systems with two different soil textures (sandy loam and sandy clay loam) in a semiarid region of Northeast China. Our results showed that poplar-based agroforestry practices affected soil MBC, POMC, and POMN, albeit there was no significant difference in TOC and TN. Agroforestry practices increased MBC, POMC, and POMN in sandy clay loam soils. However, in sandy loam soils, agroforestry practices only increased MBC and even decreased POMC and POMN at the 0- to 15-cm layer. Our results suggest that labile SOM fractions respond sensitively to poplar-based agroforestry practices and can provide early information about the changes in SOM in semiarid regions of Northeast China and highlight that the effects of agroforestry practices on labile SOM fractions vary with soil texture.     

The use of simple kinetic models to help design environmental monitoring systems

This paper describes the application of simple linear models to help design environmental monitoring systems. This process involves five steps: (1) The derivation of a schematic of the identified pollutant's transport and fate. (2) The derivation of the equation in the schematic. (3) Estimation of input data and numerical solution. (4) Comparison with initial field data. (5) Design of a monitoring system.Two examples of how this system was applied under field conditions are given. Advantages of this approach are: (1) It forces a consideration of the system as a whole rather than a series of distinct environmental components. (2) It forces a consideration of the physical-chemical and biological factors effecting pollutant transport in the system. (3) It sets up an analytical procedure for data analysis at the time the monitoring system is designed. (4) It helps show the functional relationship between pollutant levels in different environmental media. (5) It identifies points where sampling design could be changed to provide for a more efficient monitoring system. (6) It identifies gaps in our knowledge base.     

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.     

The relevance of speciation in the remediation of soils and sediments contaminated by metallic elements--an overview and examples from Central Scotland, UK

The environmental impact of metallic contaminants in soils and sediments is dependent both on the chemical speciation of the metal and the response of the matrix to biological and physicochemical conditions. These factors are responsible for the mobilisation of the metal from the solid into the aquatic phase and hence transport within the immediate vicinity, impacting on the rate of dispersal, dilution, uptake and transfer into living systems. The impact of changing environmental conditions on the contaminant inventory can be to enhance or moderate these phenomena, with subsequent consequences for the broader risk assessment of the contaminants. Remediation of metallic contaminants can only be brought about by their removal from the site or by establishing conditions which favour their retention in the solid phase. A wide range of in situ and ex situ approaches are available and a summary overview is presented. The examples show assessment at both the field and laboratory scale and demonstrate an equally wide range of success in achieving remediation targets. This can be attributed to limitations in ensuring that the desired conditions for the initial removal or immobilisation process are met and maintained over a suitable period of time. Three areas are reviewed which include: the transport and release of metallic contaminants in estuarine sediments and the assessment of their potential to impact on biota; terrestrial contamination systems involving the release of chromium from waste ore contaminating urban environments; the response of metal-contaminated wastes to changing environmental conditions and the impact of natural bioremediation. The focus of the discussion is to highlight the generation of reliable speciation information and the problems associated with impact and risk assessment. Particular issues of concern are the laboratory to field scale evaluation of contaminant behaviour and the approach used to assess the reliability of remediation options. In conclusion, part of a recent initiative in risk assessment and the development of pilot scale experimental systems to study long-term behaviour are addressed as future goals to fill gaps in current research.