The development of alum rates to enhance the remediation of phosphorus in fluvial systems following manure spills

Following the remediation of animal manure spills that reach surface waters, contaminated streambed sediments are often left in place and become a source for internal phosphorus (P) loading within the stream in subsequent flow. The objective of this study was to develop treatment rates and combinations of alum and CaCO(3) to mitigate P from contaminated sediments of different particle size distributions following a manure spill. Sediment specific alum and CaCO(3) treatment rates were developed based upon the resultant alum treatment ranges established for each sediment type. Clay loam sediments required 54% more alum to mitigate P desorption relative to sediments that contain at least 60% sand. Amending sediments with the highest rates of alum/alum + CaCO(3), resulted in a 98-100% reduction in P desorption and a similar water column pH for all sediments types. Observations from this study demonstrated the effectiveness of alum/alum + CaCO(3) to increase P retention in sediments following a manure spill.     

Distribution and accumulation of heavy metals in the sediments of Akkaya Dam,Nigde, Turkey

Twenty-one surface sediment samples were collected from Akkaya Dam. Heavy metal concentrations (Mo, Cu, Pb, Zn, Ni, Co, Mn, Fe, Cr, As, V and Cd), grain size, organic carbon and carbonate contents were studied in order to assess the extent of environmental pollution and to discuss the origin of these contaminants in sediments of dam. The sediments in the study area are mostly very fine sands. However, mud was observed in the northeast of the dam. Sediment pollution assessment was carried out using enrichment factor. The calculation of enrichment factors showed that Mo is depleted by 1.0 whereas Cu, Pb, Zn, Ni, Co, Mn, As, V, Cr and Cd are enriched by 3, 5.4, 7, 2.7, 2.2, 3.4, 42.3, 2.1, 1.8 and 7.2, respectively. Relatively high concentrations heavy metals occurred in north (textile industry area) and east (Karasu River) due to enrichment controlled by anthropogenic wastes. The results of correlation analysis show low–medium positive and negative correlations among metals, grain size, carbonate contents and organic carbon and indicate that heavy metals in sediments of the Akkaya Dam have different anthropogenic sources.     

Trace metals: Inputs, sedimentation and accumulation in San Vicente Bay, Chile

The present study deals with sediment dynamics affecting sediment-associated metal distributions in an embayment system experiencing pollution from coastal industries. Sedimentary metal content may originate from diagenetic processes of foundation rock on the bottom, allochthonous minerals from natural sources, and metals from industrial effluents along the coast. The study presents experimental estimations of quantities of metals entering the bay in industrial wastewater, measurements of metal content in particulate material captured in sediment traps, and metals distribution in surface sediments. Quantitative estimations of metals entering the system in industrial effluent showed the relation Pb Zn > Cu > Cr Ni > Cd. That of metals associated with particulate material from traps was Zn > Cr Cu > Pb > Ni > Cd and the abundance of metals in sediments was Zn > Cr > Cu > Pb > Ni > Cd. Finally, rates of bottom sediment accumulation are estimated in relation to the time of residence of water in the bay. The experimental data on sedimentation and sediment abundance were consistent with field observations on distribution and accumulation at sites of major sedimentation in this bay.     

The accumulation of metals and toxic effects in Nereis virens exposed to pulverised fuel ash

The marine polychaete worm Nereis virens was used to study the bioaccumulation patterns of metal exposures with pulverised fuel ash (PFA). Juvenile N. virens were exposed for 12 weeks to sediments comprised of 100% PFA, 50% PFA-50% clean sand, a reference sediment (contaminated harbour-dredged material) and a clean sand control. Mortality after the first 4 weeks was high at 32–45% in the four sediments. However, this declined to a few percent during the following 8 weeks. Growth expressed as biomass (wet weight) was reduced in bout PFA treatments and the reference sediment. Heavy metal accumulation in the tissues of N. virens was characterised as follows: a group of elements showed negligible to low accumulation (Cd, Cr, Ni, and Zn), As and Cu wich showed a definite, but moderate accumulation: and finally Se, which showed a low accumulation rate, where an uptake equilibrium was not reached after 9 weeks. It is concluded that acute toxic effects did not occur but a population of N. virens inhabiting a PFA dumping site could be affected by high Se concentrations.     

Biomonitoring of contaminated mine tailings through age accumulation of trace metals in the bank vole (Clethrionomys glareolus)

Lead, zinc and cadmium were determined in a range of tissues from laboratory-bred bank voles (Clethrionomys glareolus) exposed to elevated levels of dietary zinc (124 micrograms g-1). The pelletised diet was derived from vegetation harvested from the surface of a revegetated tailings dam at a modern Zn-Pb mine. Exposure regimes to the contaminated diet were 16, 32, 64, 128 or 256 days. Elevated levels of dietary zinc were not reflected in the individual tissue or total body concentrations. Marginal age accumulation of lead and cadmium was evident in the liver (Pb) and kidney (Pb and Cd). Tissue residues did not attain toxicologically significant concentrations. Animals inhabiting the grassland are considered to be at low ecotoxicological risk with respect to trace metals.     

Factors controlling the salinity in groundwater in parts of Guntur district, Andhra Pradesh, India

Groundwater chemistry has been studied to examine the associated hydrogeochemical processes operating for the development of salinity in the groundwater in parts of Guntur district, Andhra Pradesh, India. The study area is underlain by charnockites and granitic gneisses associated with schists of the Precambrian Eastern Ghats. Groundwater is the main resource for irrigation besides drinking. Chemical parameters, pH, EC, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, , , Cl⁻, , , F⁻ and SiO₂, are taken into account. Groundwater is of brackish type. Na⁺−Cl⁻ facies dominates the groundwater. Examination of compositional relations and mineral saturation states shows that the ion exchange of Ca²⁺ for adsorbed Na⁺, evapotranspiration, dissolution of soil salts, dissolution of NaCl and CaSO₄, and precipitation of CaCO₃ are the dominant hydrogeochemical processes associated with the groundwater composition in the area. Evapotranspiration causes accumulation of salts in the soil/weathered zone. These salts reach the water table by leaching through infiltrating recharge water. A positive relation between depth to water table and TDS with season supports this inference. The effects of human activities, such as intensive and long-term irrigation, irrigation-return-flow, application of unlimited agricultural fertilizers and recycling of saline groundwater, act to further increase the salinity in the groundwater. Therefore, the groundwater quality increases towards the flow path, while the post-monsoon groundwater shows higher concentrations of TDS, Na⁺, Mg²⁺, Cl⁻, , , F⁻ and SiO₂ ions. The study could help to understand the hydrogeochemical characteristics of the aquifer system for taking effective management measures to mitigate the inferior groundwater quality for sustainable development.     

Fractionation and potential mobility of trace metals in Danube alluvial aquifer within an industrialized zone

Thirty-five alluvial sediments of the River Danube and 12 groundwater samples were taken within the Pan?evo Oil Refinery (Serbia). The results for groundwater samples exceed European primary drinking water standards for Fe (obtained results, >200 μg/l) and Mn (obtained results, >50 μg/l), while the levels of the trace metals are below the thresholds for drinking water quality. Sediments were treated by sequential extraction procedure with five different solutions, each having a higher extraction capacity than the previous one. We also wanted to determine the possible relationships among trace metals and between sediment properties and elemental concentrations. These solutions partitioned metals into CH₃COONH₄ extractable (F1); HCl carbonate extractable and NH₂OH·HCl easily reducible (F2); (NH₄)₂C₂O₄/H₂C₂O₄ moderately reducible (F3); H₂O₂–HNO₃ organic/sulfide extractable fractions (F4); and HCl acid-soluble residue (F5). The sum of trace metals Ni, Pb, Cu, and Zn associated with the first two fractions (exchangeable, carbonate, and easily reducible) is significant and extremely important because it represents the proportion of heavy metals that can be easily remobilized by changes in environmental conditions such as pH, redox potential, salinity, etc. Sediments located nearer the groundwater flow are exposed to stronger groundwater fluctuation and had a higher quantity of amorphous and less stable substrates of trace metals. Principal component analysis was used to understand and visualize the associations between the trace metals and certain geological forms within analyzed sediments. The observed association between Cr with total sulfur and Mn from the acid-soluble residue could indicate that Cr is in the form of reduced, less toxic Cr(III), which is from the ecochemical point of view very important.     

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.     

Remote in situ voltammetric techniques to characterize the biogeochemical cycling of trace metals in aquatic systems

The contamination of aquatic ecosystems by natural and anthropogenic metals has lead to a need to better characterize their impact in the environment. To a large extent, the fate and the (eco)toxicity of these elements in aquatic systems are related to their chemical speciation, which may vary continuously in space and time. Detailed measurements of the fraction of specific metal species or groups of homologous metal species and their variation as a function of the bio-physicochemical conditions of the natural media are thus of prime importance. To determine these metal fractions as well as redox chemical species regulating their distribution (dissolved oxygen, sulfides, iron and manganese oxides), new analytical tools capable of performing in situ, real-time monitoring in both water columns and sediments with minimum perturbation of the media are required. This paper reviews the challenges associated with metal speciation studies, and the progress made with state of the art voltammetric techniques to measure the speciation of metals in situ. More specifically, it summarizes the specific conceptual, analytical, and technical criteria that must be considered and/or fulfilled to develop rugged, field deployable, non-perturbing sensors and probes. Strategies used to satisfy these criteria are presented by describing the up-to-date most advanced voltammetric sensors, mini-/micro-integrated analytical systems, and submersible equipments developed for in situ measurements of trace metals and main redox species in aquatic systems. The spatial and temporal resolutions achieved by these news tools represent a significant advantage over traditional laboratory techniques, while simultaneously remaining cost effective. The application of these tools to aquatic systems is illustrated by several examples of unattended and remote in situ monitoring and/or profiling in water columns and sediments.     

Conventional, microwave, and ultrasound sequential extractions for the fractionation of metals in sediments within the Petrochemical Industry, Serbia

In this paper, the main objective was fractionation of Cd, Cu, Ni, Pb, Zn, Ca, Fe, and K in certificate material and sediment samples gathered from and around the Petrochemical Industry using the conventional, microwave and ultrasonic sequential extraction. Microwave oven and ultrasound bath were used as an energy source for achieving faster extraction. Additional heating and boiling of samples were avoided by using lower power and shorter time for microwave and ultrasound extraction. Precision and accuracy of procedure were evaluated by using certificate material (BCR701). Acceptable accuracy of metals (87.0–111.3 %) was achieved for all three-step sequential of conventional extraction protocol. An accuracy of the fourth step has been verified with two certificate materials: BCR143R and 146R. The range of total extracted metal concentrations from sediments was similar for all three extraction techniques. A significant high percentage of Cd, Cu, and Zn were obtained after extraction of the exchangeable and acid soluble sediment fraction. Principal component analysis of values obtained after determination of risk assessment code using conventional and ultrasound sequential extraction show similarity of these values. Accuracy, recovery, and risk assessment code values imply that ultrasound sequential extraction is a more suitable, accelerated sequential extraction procedure (30 min per extraction step) than microwave extraction in applied conditions.     

Bricks as historical record of heavy metals fallout: Study on copper accumulation in Agra soils since 1910

Peat, ice deposits and aquatic sediments, which have been used as a geochemical monitor of atmospheric heavy metal pollution until now, are open and dynamic systems and can be easily affected by climatic variations. In contrast, bricks, which are more compact, can act as a better geochemical monitor. Analysis of Cu, Cr, Ni, Pb and Zn in scores of soil and brick (baked/unbaked) samples, collected from a large area in and around a rapidly growing Indian city, Agra, reveals approximately similar concentrations in soils and bricks, thereby showing insignificant fractionation of these metals during brick making. Further, metals concentration in the core of bricks remains unaffected by any significant amount of acidic and alkaline rain. Thus, the feasibility of a novel role of bricks as a geochemical monitor of atmospheric heavy metal pollution has been tested. Utilizing this concept, an attempt has also been made to trace the history of atmospheric copper depositions in the soils of Agra during the last 100 years.     

Impacts of the fish farms on the water column nutrient concentrations and accumulation of heavy metals in the sediments in the eastern Aegean Sea (Turkey)

Pulp and paper mill effluents may cause harmful effects to the aquatic environment due to the combined influence of physical factors, toxic compounds, and nutrient enrichment. In the present study, the effectiveness of secondary treatment in reducing the toxicity of an elemental chlorine-free bleached-kraft pulp mill effluent was evaluated. To characterize the toxicity of the effluent, before and after the implementation of secondary treatment, a battery of tests with organisms bearing different functions at the ecosystem level was used, namely Vibrio fischeri (5-min luminescence), Pseudokirchneriella subcapitata (72-h growth), Lemna minor (7-day growth), Daphnia magna (21-day reproduction and 24-h postexposure feeding), Chironomus riparius (9-day growth), and Danio rerio (28-day growth). For the effluent sample collected before the implementation of secondary treatment, P. subcapitata was the most sensitive organism followed by V. fischeri and D. magna, and no toxic effects were observed toward the other organisms. For the effluent sample collected after the implementation of secondary treatment, the effluent caused no toxic effects on any of the tested species. The present results demonstrated not only that secondary treatment efficaciously reduced effluent toxicity toward the selected test organisms but also the usefulness of a battery of tests to characterize the toxicity of pulp mill effluents.     

Ecotoxicity of fluvial sediments downstream of the Ajka red mud spill, Hungary

An integrated assessment of biological activity and ecotoxicity of fluvial sediments in the Marcal river catchment (3078 km(2)), western Hungary, is presented following the accidental spill of bauxite processing residue (red mud) in Ajka. Red mud contaminated sediments are characterised by elevated pH, elevated trace element concentrations (e.g. As, Co, Cr, V), high exchangeable Na, and induce an adverse effect on test species across a range of trophic levels. While background contamination of the river system is highlighted by adverse effects on some test species at sites unaffected by red mud, the most pronounced toxic effects apparent in Vibrio fischeri bioluminescence inhibition, Lemna minor bioassay and Sinapis alba root and shoot growth occur at red mud depositional hotspots in the lower Torna Creek and upper Marcal. Heterocypris incongruens bioassays show no clear patterns, although the most red mud-rich sites do exert an adverse effect. Red mud does however appear to induce an increase in the density of aerobic and facultative anaerobic bacterial communities when compared with unaffected sediments and reference sites. Given the volume of material released in the spill, it is encouraging that the signal of the red mud on aquatic biota is visible at a relatively small number of sites. Gypsum-affected samples appear to induce an adverse effect in some bioassays (Sinapis alba and Heterocypris incongruens), which may be a feature of fine grain size, limited nutrient supply and greater availability of trace contaminants in the channel reaches that are subject to intense gypsum dosing. Implications for monitoring and management of the spill are discussed.     

The burrowing crab Neohelice granulata as potential bioindicator of heavy metals in estuarine systems of the Atlantic coast of Argentina

This paper presents the concentrations of total copper, lead, cadmium, and zinc in hepatopancreas of the burrowing crab Neohelice granulata from the Samboromb??n Bay (La Plata River estuary) and the Mar Chiquita coastal lagoon, Argentina. The highest accumulation of lead was observed in Mar Chiquita samples, whereas copper, zinc, and cadmium concentrations were higher in those from Samboromb??n Bay. Marked temporal and geographic availability differences were observed, while sexual differences only were observed for zinc. Finally, the validity of using this species as bioindicator of heavy-metal pollution within the assessed estuarine ecosystems is discussed.     

Bacteria with dual resistance to elevated concentrations of heavy metals and antibiotics in Nigerian contaminated systems

Samples of soil, water, and sediments from industrial estates in Lagos were collected and analyzed for heavy metals and physicochemical composition. Bacteria that are resistant to elevated concentrations of metals (Cd^2?+?, Co^2?+?, Ni^2?+?, Cr^6?+?, and Hg^2?+?) were isolated from the samples, and they were further screened for antibiotic sensitivity. The minimum tolerance concentrations (MTCs) of the isolates with dual resistance to the metals were determined. The physicochemistry of all the samples indicated were heavily polluted. Twenty-two of the 270 bacterial strains isolated showed dual resistances to antibiotics and heavy metals. The MTCs of isolates to the metals were 14 mM for Cd^2?+?, 15 mM for Co^2?+? and Ni^2?+?, 17 mM for Cr^6?+?, and 10 mM for Hg^2?+?. Five strains (Pseudomonas aeruginosa, Actinomyces turicensis, Acinetobacter junni, Nocardia sp., and Micrococcus sp.) resisted all the 18 antibiotics tested. Whereas Rhodococcus sp. and Micrococcus sp. resisted 15 mM Ni^2?+?, P. aeruginosa resisted 10 mM Co^2?+?. To our knowledge, there has not been any report of bacterial strains resisting such high doses of metals coupled with wide range of antibiotics. Therefore, dual expressions of antibiotics and heavy-metal resistance make the isolates, potential seeds for decommissioning of sites polluted with industrial effluents rich in heavy metals, since the bacteria will be able to withstand in situ antibiosis that may prevail in such ecosystems.     

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.     

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.     

Single and mixture effects of pesticides and a degradation product on fluvial biofilms

The Morcille River located in the Beaujolais vineyard area (Eastern France) is subjected to strong vine-growing pressure leading to the contamination by a range of herbicides and fungicides of the surrounding freshwater environment. Particularly high concentrations of norflurazon, desmethyl norflurazon and tebuconazole were recorded in spring 2010 at the downstream site of the river. Despite their occurrence in rivers, scarce toxicity data are available for these products, in particular in the case of desmethyl norflurazon (main norflurazon degradation product). Furthermore, the toxicity data are generally available only for single compounds and are issued from single species toxicity tests, leading to a lack of ecological relevance. Consequently, this study was undertaken to evaluate the toxic effects of norflurazon, desmethyl norflurazon and tebuconazole singly and in a ternary mixture on fluvial biofilm. Toxicity tests were performed in microplates for 48 h. Photosynthetic endpoints were measured using pulse amplitude-modulated fluorometry; diatom densities and taxonomic composition were determined. After 48 h of exposure, significant effects on optimal quantum yield (F _v/F _m) for desmethyl norflurazon and mixture were observed.