The occurrence of 16 pharmaceutical compounds in river sediments from Donana National Park was investigated, as well as the ecotoxicological risk to the ecosystems of this well-known protected zone. Eight of the 16 pharmaceuticals were present in sediments. The highest concentrations in river sediments concern to diclofenac, salicylic acid and caffeine (52.1, 27.2 and 25.4 mu g/kg dm). Naproxen, carbamazepine, propranolol, 17 beta-estradiol and estriol were the other pharmaceutical compounds detected in sediment samples. The relation between the concentration of these pharmaceutical compounds in sediments and river water in contact with was also investigated. While some compounds were detected exclusively in sediment samples (diclofenac, 17 beta-estradiol and estriol), others were detected only in surface waters in contact with (ibuprofen, ketoprofen and gemfibrozil). The outcome analyses of the ecotoxicological risk assessment showed that the presence of all studied pharmaceutical compounds involved a high toxicological risk at short and long term to Donana ecosystem.

The Pennask Creek watershed in British Columbia (BC), Canada has been contaminated with acid rock drainage (ARD) and associated metal leaching (ML) as a result of highway construction. By combining existing and newly gathered information, this study determined the extent of metal contamination of the water and sediments, the potential biological impacts of this contamination, the influence of local geology, and estimated the potential risk to aquatic organisms. Surface water and sediment samples from the watershed were analyzed for general chemical parameters and trace metals. Rock samples were analyzed for mineralogy and chemical composition. Metal concentrations in water and sediments downstream of the ARD/ML source were higher than elsewhere in the watershed. Metals of concern include aluminum (Al), copper (Cu), and zinc (Zn). Analysis of historical water quality data indicated that the concentrations of these metals have decreased markedly since 2004, due to remediation efforts. Rock samples collected from the streambeds and banks were not found to be potentially acid generating, but did contain significant levels of metals. Al, Cu, and Zn levels consistently exceeded BC water and sediment quality guidelines for the protection of aquatic life, indicating that adverse biological effects are probable at stations downstream of the ARD/ML source. Benthic invertebrate monitoring over a 10-year period showed low abundance and diversity and a complete absence of sensitive taxa at downstream stations. Risk quotients indicated a likelihood of adverse biological effects for aquatic organisms, including rainbow trout, due to metal contamination in the watershed.

Acid mine drainage (AMD) has long been a significant environmental problem that impairs water resources in historic or current mining industries throughout the world. One of the methods using passive treatment system at low cost to remove metals from solution involves the use of clays. The ability of three different adsorbents (montmorillonite K-10, bentonite (NT-25), and hydrotalcite (HT)) to remove Fe and Mn from aqueous solutions and acid mine drainage samples has been studied at different optimized conditions such as pH, amount of adsorbent and contact time. Flame atomic absorption spectrometer (FAAS) was used for measuring Fe and Mn concentrations. Langmuir and Freundlich isotherms were applied and isotherm coefficients were computed. A kinectic study was also developed for HT using the first order, second order and intraparticle diffusion models. A great amount of clay (more than 100 mg) and also contact times higher than 60 min had also no influence in the adsorption capacity for all adsorbents. HT was found to be the best among the studied clays removing more than 90 % of Fe and Mn for all AMD samples investigated. Moreover, the maximum adsorption capacity was 63.7 mg Mn g⁻¹ HT and 666.7 mg Fe g⁻¹ HT.

Land use in east China tends to change from paddy rice to vegetables or other high-value cash crops, resulting in high input rates of organic manures and increased risk of contamination with both heavy metals (HMs) and antibiotics. This investigation was conducted to determine the accumulation, distribution and risks of HMs and tetracyclines (TCs) in surface soils and profiles receiving different amounts of farmyard manure. Soil samples collected from suburbs of Hangzhou city, Zhejiang province were introduced to represent three types of land use change from paddy rice to asparagus production, vineyards and field mustard cultivation, and divided into two portions, one of which was air-dried and sieved through 2-, 0.3- and 0.149-mm nylon mesh for determination of pH and heavy metals. The other portion was frozen at -20 °C, freeze-dried and sieved through a 0.3-mm nylon mesh for tetracyline determination. HM and TC concentrations in surface soils of 14-year-old mustard fields were the highest with total Cu, Zn, Cd and ∑TCs of 50.5, 196, 1.03 mg kg(-1) and 22.9 μg kg(-1), respectively, on average. The total Cu sequence was field mustard > vineyards > asparagus when duration of land use change was considered; oxytetracycline (OTC) and doxycycline were dominant in soils used for asparagus production; OTC was dominant in vineyards and chlortetracycline (CTC) was dominant in mustard soils. There were positive pollution relationships among Cu, Zn and ∑TCs, especially between Cu and Zn or Cu and ∑TCs. Repeated and excessive application of manures from intensive farming systems may produce combined contamination with HMs and TCs which were found in the top 20 cm of the arable soil profiles and also extended to 20-40 cm depth. Increasing manure application rate and cultivation time led to continuing increases in residue concentrations and movement down the soil profile.

During this study, we investigated the mineralogical characterization of technogenic magnetic particles (TMPs) contained in alkaline industrial dust and fly ash emitted by coal burning power plants and cement plants. The reaction of tested dust samples varied between values of pH 8 and pH 12. Their magnetic properties were characterized by measurement of magnetic susceptibility (χ), frequency dependence of magnetic susceptibility (χfd), and temperature dependence of magnetic susceptibility. Mineralogical and geochemical analyses included scanning electron microscopy with energy dispersive spectroscopy, microprobe analysis and X-ray diffraction. The TMPs in fly ash from hard coal combustion have the form of typical magnetic spherules with a smooth or corrugated surface as well as a skeletal morphology, composed of iron oxides (magnetite, maghemite, and magnesioferrite) that occurred in the form of incrustation on the surface of mullite, amorphous silica, or aluminosilicate particles. The TMPs observed in fly ash from lignite combustion have a similar morphological form but a different mineralogical composition. Instead of magnetite and magnesioferrite, maghemite and hematite with lower χ values were the prevailing magnetic minerals, which explains the much lower magnetic susceptibility of this kind of ash in comparison with the ash from hard coal combustion, and probably results from the lower temperature of lignite combustion. Morphology and mineralogical composition of TMPs in cement dust is more diverse. The magnetic fraction of cement dust occurs mostly in the form of angular and octahedral grains of a significantly finer granulation (<20 μm); however, spherules are also present. A very characteristic magnetic form for cement dust is calcium ferrite (CaFe₃O₅). The greatest impact on the magnetic susceptibility of cement dust results from iron-bearing additives (often waste materials from other branches of industry), which should be considered the most dangerous to the environment. Stoichiometric analysis of micro-particles confirmed the presence of heavy metals such as Pb, Mn, Cd, and Zn connected with TMPs, which are carriers of magnetic signals in atmospheric dust. Therefore, in some cases, their presence in topsoil when detected by magnetic measurement can be treated as an indicator of inorganic soil contamination.

In this study, we investigate the corrosion effects on modern materials at various sheltered and unsheltered locations in the Greater Athens Area (GAA) due to atmospheric pollution, since materials deterioration could emerge severe economic costs in the near future. The preselected materials are weathering steel, copper, bronze, zinc, and aluminum, which are mainly used in modern constructions in the GAA. The method applied in this study leads in the production of corrosion maps for GAA in the period 2000–2009 by using sophisticated geoanalytical methods together with dose–response functions for the selected materials. The corrosion effects are significant for weathering steel, moderate for copper and bronze and weak for zinc and aluminum. Also, a corrosion trend analysis is performed, which can be a very helpful tool for future protection of such materials from atmospheric pollution. The results show increasing corrosion trends for weathering steel and copper in the eastern regions of GAA, probably caused by the recent operation of the Athens International Airport at Spata, while no corrosion trends were observed to the other materials. The method applied in this work provides comprehensive results for the estimation of the impact of atmospheric corrosion on various construction materials.

Parameters known to influence mercury (Hg) release from soils include substrate and air Hg concentration, light, atmospheric oxidants, temperature, and soil moisture. However, for low Hgcontaining soils, the influence of these parameters has been shown to vary across space and time. Here, we expand upon previous work by investigating whether soil-water evaporative loss, which integrates the influence of multiple parameters, could be applied for predicting Hg flux from soil with low Hg concentrations when bare and planted. To investigate our hypothesis, Hg flux was measured from three soil types (<100 ng Hg g-1). When these soils were saturated, flux was suppressed. Soil moisture evaporative stage was used to partition the parameters most important for controlling Hg flux as the soils dried. Classification and regression tree (CART) analyses showed that soil moisture was the most important parameter predicting Hg flux. Results also showed an important predictor for Hg flux was whether actual evaporation (Ea) was equal to potential evaporation (Ep) or Ea < Ep. Depending on evaporative stage, the parameters with the next highest correlation to Hg flux were light, temperature, and soil moisture evaporation rate. The presence of vegetation also influenced flux with lower Hg flux when the plants were transpiring. Results indicate for those developing models that estimate Hg flux from low Hg-containing soils, soil moisture and evaporative stage are useful tools for predicting flux. © Springer Science+Business Media Dordrecht 2013.

Kinetics and mechanism on discoloration of an azo dye, methyl orange (MO), by heterogeneous Fenton-like reaction using natural schorl as catalyst were investigated in this study. Among the three kinetic models (the first-order, the second-order, and the Behnajady-Modirshahla-Ghanbery (BMG)), the BMG kinetic model was the best one to describe MO discoloration at different reaction conditions, due to its highest determination coefficients. The BMG model parameter, 1/m, increased with initial hydrogen peroxide (H2O 2) concentration, and schorl dosage and reaction temperature increased while the pH solution decreased. The phenomenon indicated that the initial MO discoloration rate increased with the ascending of the initial H 2O2 concentration, schorl dosage, and reaction temperature and the descending of the pH solution. Meanwhile, another BMG parameter, 1/b, except for the one at pH=5, were all around 1, implying that the schorl-catalyzed Fenton-like reaction had high capacity for MO discoloration. The possible reason for these phenomena was interpreted from the point of view of OH generation and Fe dissolution. Generally speaking, the amount of hydroxyl radicals increased with initial H2O2 concentration, increased schorl dosage and reaction temperature, and decreased pH solution, playing an important role in the change of 1/m values. The concentration of soluble iron ions at all adopted experimental conditions ranged from 0.23 to 1.14 mg/L, much lower than the European Union directive (2 mg/L), which demonstrated that natural schorl would be a promising heterogeneous catalyst for the Fenton-like reaction. Finally, a possible mechanism for this process was put forward. © Springer Science+Business Media Dordrecht 2013.

Soil is one of the compartments most affected by the accumulation of pollutants from anthropic sources. The present study allowed the identification of the sensitivity of the Allium cepa test system to evaluate solubilized soils from two points in the area contaminated by heavy metals, as well as a point of reference. They are all located in the municipality of Triunfo, state of Rio Grande do Sul, Brazil. The parameters used for evaluation were germination index, mitotic index, chromosomal aberrations (CA), and index of mutagenicity index (IMUT) presented by A. cepa. Significant responses of CA were observed in the two samples of contaminated soil, but IMUT was significant only for soil 3. The toxicity and cytotoxicity indexes did not show significant responses. The results indicate that the A. cepa plant test system was sensitive to investigate the genotoxicity of the soil samples and can be used as an alert in studies on soil contamination. It was partially concordant with the mutagenic responses already detected for the Salmonella/microsome assay in previous studies.

Biochar has great potential as a soil amendment to immobilize heavy metals, thereby reducing their bioavailability. In this study, biochars derived from chicken manure and green waste were compared with commercial activated carbon (AC) and laboratory produced black carbon (BC) for the sorption of Pb and Cd. Sorption kinetics and equilibrium sorption isotherms for Pb and Cd were obtained for the char materials and the data were fitted to kinetic and sorption isotherm models. Chicken manure-derived biochar (CM) showed the highest sorption capacity for both Pb and Cd, and the Pb sorption by biochars was higher than the Cd sorption because of the precipitation of Pb with various ions released from the biochars such as carbonate, phosphate, and sulfate. The sorption data for both Pb and Cd were better represented by the pseudo-second order kinetic model than the pseudo-first order kinetic model, which indicates chemical sorption between biochar and metals. For the isotherm studies, char materials was mixed with various amount of Pb or Cd solutions and the remaining metal concentration was measured. The equilibrium sorption data followed a Langmuir isotherm with a maximum sorption capacity of 6.8-11 and 1.7-8.0 mg/g by biochars for Pb and Cd, respectively. Furthermore, CM immobilized Pb and Cd up to 93.5 and 88.4 %, respectively, while BC was not effective in the immobilization of Pb in soil. Overall, the sorption experiments in solution and the immobilization experiment in soil showed that biochars are more effective than AC in the sorption of Pb and Cd, and that they have the potential to be used as a soil amendment to remediate metal-contaminated soil. © 2013 Springer Science+Business Media Dordrecht.