Groundwater contamination evolution in the Guadiamar and Agrio aquifers after the Aznalcóllar spill: assessment and environmental implications

In 1998, the Agrio and Guadiamar rivers underwent an enormous environmental disaster caused by the rupture of the Aznalcóllar tailings dam and the release of 6 hm³ of pyrite sludge and acidic water. Both rivers run over recent alluvial materials which form a small-sized aquifer which is however important because underground water feeds the flow of the rivers. This work analyzes the state of groundwater 10 years after the spill. Before the dam failure, this aquifer was already contaminated in the zone nearest to the mine, to which the impact of the spill was added. Contamination levels in the alluvial aquifer of the Agrio River have decreased remarkably. However, they are still important, with acidic pH values and high concentrations of toxic elements (maximum values of 16 mg/L of Zn and 15 mg/L of Al). There are also important levels of contamination in the Guadiamar alluvial area closest to the mine, as well as in specific zones located further south. The concentration of toxic elements is mainly controlled by pH. The evolution of contaminant levels show a sharp decrease after the first years following the spill, followed by a subsequent stabilization. It is necessary to take measures for the recovery of the aquifer because, otherwise, groundwater will continue contributing contaminants into the Agrio and Guadiamar rivers.     

Development of geomorphologic instantaneous unit hydrograph for a large watershed

Hill torrents cause a lot of environmental and property damage in Pakistan every year. Proper assessment of direct runoff in the form of hill torrents is essential for protection of environment, property, and human life. In this paper, direct surface runoff hydrograph (DSRH) was derived for a large catchment using the geomorphologic instantaneous unit hydrograph concept. The catchment with hill torrent flows in semi-arid region of Pakistan was selected for this study. It was divided into series of linear cascades and hydrologic parameters required for Nash's conceptual model, and were estimated using geomorphology of the basin. Geomorphologic parameters were derived from satellite images of the basin and ERDAS and ArcGIS were used for data processing. Computer program was developed to systematically estimate the dynamic velocity, its related parameters by optimization and thereby to simulate the DSRH. The data regarding rainfall-runoff and satellite images were collected from Punjab Irrigation and Power Department, Pakistan. Model calibration and validation was made for 15 rainfall-runoff events. Ten events were used for calibration and five for validation. Model efficiency was found to be more than 90% and root mean square error to be about 5%. Impact of variation in model parameters (shape parameter and storage coefficient) on DSRH was investigated. For shape parameter, the number of linear cascades varied from 1 to 3 and it was found that the shaper parameter value of 3 produced the best DSRH. Various values of storage coefficient were used and it was observed that the value determined from geomorphology and the dynamic velocity produced the best results.     

A survey on the utility of the USEPA CADDIS stressor identification procedure

The Environmental Protection Agency (EPA) has made available on the worldwide web a systematic stream stressor identification procedure, the “Causal Analysis/Diagnosis Decision Information System” or CADDIS. We report here the results of a survey of regulators and scientists in 11 states who use CADDIS or another stressor identification procedure in their work. The 13 survey questions address guidelines as to what impairment scenarios to approach with stressor identification, what information is needed to perform stressor identification, and what the stakeholder role is in performing stressor identification. At the time of this survey (the summer of 2009), the EPA CADDIS website was less commonly used among the state regulators surveyed than the published EPA stressor identification document on which it is based. The respondents generally find the EPA stressor identification procedure useful and capable of being adapted to their individual needs. Survey respondents all use stressor identification in their Total Maximum Daily Load work, but also in a wide variety of other applications. All the “types of evidence” included in the CADDIS stressor identification procedure are used by the practitioners surveyed with the exception of the results of ecological simulation models. While the CADDIS documentation encourages the involvement of stakeholders in stressor identification, most respondents do not assemble stakeholder teams of local officials and citizens to participate in stressor analyses.     

Chemical dynamics of the Sava riverine system

Presented here is a study of the geochemical dynamics of the entire River Sava watershed, a major tributary of the River Danube which has not previously been investigated. The sampling was performed at 33 selected locations along the main channel of the stream and at its largest tributaries during three sampling seasons (fall 2005, spring 2006 and fall 2006), going from headwater locations to the mouth near the confluence with the Danube. Almost 80% of the solutes are derived from carbonate mineral weathering and represent over 50% of specific HCO(3)(-) flux normalized to unit basin area at the mouth of the Danube. Statistical analysis indicates that agricultural and industrial sources contribute significantly to increased Na(+), K(+), Cl(-), SO(4)(2-) and NO(3)(-) concentrations in tributary waters. Different processes control the water chemistry along the course of the Sava's drainage-the upper reaches are largely regulated by contributions from carbonate mineral weathering, the middle reaches are influenced by agricultural activity and biological processes related to eutrophication, while the lower reaches tend to have more pronounced parameters related to the industrial processing along with leakages from municipal sanitary systems of these higher population density areas.     

Sand as a relevant fraction in geochemical studies in intertidal environments

Soil and sediment samples from several intertidal environment exposed to different types of contamination were studied to investigate the importance of grain size in relation to the capacity of the substrates to retain trace metals. The unfractionated samples (referred to as bulk samples) were separated into the following grain/size fractions: fine–coarse sand (2?0.100 mm), very fine sand (0.100?0.050 mm), silt (0.050?0.002 mm), and clay (0.002 mm). The sample into its fractions was carried out was in a glove box under high-purity N₂ atmosphere in order to minimize any alterations to the samples. The bulk samples were characterized in terms of physicochemical properties such as pH, redox potential, and grain size. The total organic carbon (TOC), total sulfur (S), iron (Fe) pyrite, Fe, and manganese (Mn), and trace metals lead (Pb), mercury (Hg), chromium (Cr), and nickel (Ni) were analyzed in the bulk samples and in each fraction. The sand fractions were also examined by scanning electron microscopy (SEM). Comparisons of the above parameters were made between fractions and between each fraction and the corresponding bulk sample. The fine–coarse sand fraction contained high levels of the primary elements of the geochemical processes that occur in marine sedimentary environments such as TOC, total Fe, Mn, and S. The net concentrations of these four elements were higher in the fine-coarse sand fraction than in the very fine sand fraction and were similar to the net concentrations in the silt and clay fractions. Detailed SEM analysis of the sand coarse fraction revealed the presence of Fe and aluminum oxyhydroxide coatings in the oxic layers, whereas the framboidal pyrites and coatings observed in the anoxic layers were Fe sulfides. The presence of the various coatings explains why the trace metal concentrations in the sand fine–coarse fraction were similar to those in the clay fraction and higher than those in the very fine sand fraction. The present results highlight the importance of the sand fraction, which is generally disregarded in geochemical and environmental studies of sedimentary layers.     

The responses of the hepatosomatic index (HSI), 7-ethoxyresorufin-O-deethylase (EROD) activity and glutathione-S-transferase (GST) activity in sea bass (Dicentrarchus labrax, Linnaeus 1758) caged at a polluted site: implications for their use in environmental risk assessment

The present study investigates the response of three hepatic biomarkers in adult sea bass (Dicentrarchus labrax, Linnaeus 1758) caged at a wastewater outlet of an oil refinery with fish caged at a pristine site used as controls. The biomarkers that were investigated were the hepatosomatic index (HSI), 7-ethoxyresorufin-O-deethylase (EROD) activity and glutathione-S-transferase (GST) activity. In addition, we have measured the levels of polycyclic aromatic hydrocarbons (PAHs) and selected heavy metals (lead, cadmium, mercury, copper and zinc) in sediment samples at the polluted site. Although the polluted site had high environmental levels of PAHs and heavy metals, there was no difference in hepatic EROD activity and HSI between fish caged at the polluted site and controls. On the other hand, GST activity was significantly lower in fish caged at the polluted site compared to controls. Our results point out that the studied biomarkers have limited use in environmental risk assessment studies, at least when caged adult sea bass is used as the sentinel species and complex toxicant mixtures are involved.     

Excitation–emission matrices applied to the study of urban effluent discharges in the Chubut River (Patagonia, Argentina)

Natural and contaminated waters of the final reaches of the Chubut River (Patagonia, Argentina) were studied to obtain information about river organic matter and effects of domestic and industrial discharges (fishery effluents and sewages). Fluorescence Excitation–Emission Matrices (EEMs) were obtained from samples only filtered (0.45 μm) and diluted, if necessary, to avoid the inner filter effect. In addition, physicochemical parameters were measured to know the quality of the water and the effluents. Results show that EEMs allow a rapid and simple control of the effluents from fisheries and domestic sewage in Chubut River estuary, necessary to take management decisions.     

Suspended particulate matter estimates using optical and acoustic sensors: application in Nestos River plume (Thracian Sea,North Aegean Sea)

The present study investigates the use of combined methods of optical and acoustic sensors, in collaboration with direct in situ measurements, for the calibration and validation of a model transforming acoustic backscatter intensity series into suspended particulate matter (SPM) concentration datasets. The model follows previously elaborated techniques, placing particular attention to the parameterization of the acoustic absorption index as a function of water physical properties. Results were obtained from the annual deployment (during 2007–2008) of an upward-facing acoustic Doppler current profiler (ADCP) (307 kHz), equipped with a Wave Array, and an optical backscatter sensor (OBS), at the bottom of Thassos Passage near Nestos River plume (Thracian Sea, Northern Greece). The OBS was calibrated through linear regression, using 2007 and 2012 field sampling data, exhibiting an error of 13–14 % due to chlorophyll presence. The ADCP signal was calibrated through simultaneous measurements of backscatter intensity and turbidity profiles. Harmonic analysis on the model-produced SPM concentrations explained the tidal influence on their variability, especially during the summer. Empirical orthogonal functions analysis revealed the impact of waves and wave-induced currents on SPM variability. Finally, Nestos River sediment load was found uncorrelated to the SPM change in Thassos Passage, due to the dispersal and sediment deposition near the river mouth.     

Statistical characteristics of selected elements in vegetables from Kosovo

Zinc, copper, iron, chromium and cobalt are essential elements for human health, showing toxicity only in high concentrations, while lead and cadmium are extremely toxic even as traces. Therefore, it is important to monitor the contents of toxic metals in vegetables. Large number of vegetables is grown and used in nutrition, in Kosovo. The concentrations of selected elements in vegetables (radish, onion, garlic and spinach) from Kosovo were determined using ICP-OES method. Oral intake of metals and health risk index were calculated. Statistical analysis indicated numerous positive correlations between concentrations of selected elements in vegetables. As a result of principal component analysis, 15 new variables were obtained which were characterized by eigenvalues. The sequence of health quotients for the heavy metals followed the decreasing order Zn?=?Mn?>?Pb?>?Cu?>?Ni?>?Fe?>?Cd?>?Co?>?Cr. The health quotients for all investigated heavy metals were below 1 (one), which is considered safe. The vegetables from Kosovo are mainly safe for use in everyday diet.     

Systematic evaluation of dissolved lead sorption losses to particulate syringe filter materials

Distinguishing between soluble and particulate lead in drinking water is useful in understanding the mechanism of lead release and identifying remedial action. Typically, particulate lead is defined as the amount of lead removed by a 0.45-μm filter. Unfortunately, there is little guidance regarding selection of filter membrane material and little consideration to the possibility of the sorption of dissolved lead to the filter. The objective of this work was to examine the tendency of 0.45-μm syringe filter materials to adsorb lead. Tests were performed with water containing 40 and 24 μg/L soluble lead at pH 7 buffered with 50 mg C/L dissolved inorganic concentration (DIC). The amounts of lead sorbed greatly varied by filter, and only two filter types, polypropylene and mixed cellulose esters, performed well and are recommended. Great care must be taken in choosing a filter when filtering soluble lead and interpreting filter results.