Occurrence and distribution of pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain

The occurrence of 43 pharmaceuticals belonging to predominant therapeutic classes and their distribution in surface water, suspended solids and sediments has been investigated in the Ebro river basin in the Northeast of Spain. WWTP effluents were found to be a main source of contamination and the spatial distribution was affected by the river flow at the sampling point and corresponding dilution factor, resulting in higher concentrations and higher loads in small tributary rivers than in the Ebro river. The study showed that some compounds are preferentially found bound to suspended solids and not detected in river water. Generally, compounds with basic characteristics (pKa > 7) showed higher tendency to bind to suspended solids. The sediment samples generally presented lower concentrations than suspended solids.     

Implications of geographic variability on Comparative Toxicity Potentials of Cu, Ni and Zn in freshwaters of Canadian ecoregions

Current methods of estimating potential environmental impacts of metals in hazard and Life Cycle Impact Assessment (LCIA) do not consider differences in chemistry and landscape properties between geographic sites. Here, we developed and applied a model for regional aquatic impact characterization of metals using an updated method for estimating environmental fate factor (FF), bioavailability factor (BF) and aquatic ecotoxicity factor (EF). We applied the model to analyze differences in Comparative Toxicity Potentials (CTPs) of Cu, Ni and Zn for 24 Canadian ecoregions. The combined impacts of regional variability in ambient chemistry (in particular DOC, pH and hardness) and landscape properties (water residence time) can change the CTPs of these metals for freshwater by up to three orders of magnitude and change the relative ranking of metal hazard between ecoregions. Variation among Canadian freshwater chemistries and landscape characteristics influence the FFs within two orders of magnitude, BFs within two orders of magnitude for Ni and Zn and four orders of magnitude for Cu, and EFs within one order of magnitude. Sensitivity of metal FFs to environmental parameters alone spans three orders of magnitude when a constant water chemistry was used for all ecoregions. These results indicate that application of regionalised metal CTPs can have a significant influence in the analysis of ecotoxicological impacts in the life cycle assessment of products and processes.     

Nitrous oxide and methane emission from a flooded rice field as influenced by separate and combined application of herbicides bensulfuron methyl and pretilachlor

Combination of divergent active principles to achieve broad-spectrum control is gaining popularity to manage the weed menace in intensive agriculture. However, such application could have non-target impacts on the soil processes affecting soil ecology and environmental interactions. A field experiment was conducted to investigate the impact of separate and combined applications of herbicides bensulfuron methyl and pretilachlor on the emission of N₂O and CH₄, and related soil and microbial parameters in a flooded alluvial field planted to rice cv Lalat. Single application of the herbicide bensulfuron methyl or pretilachlor resulted in a significant reduction of N₂O and CH₄ emissions while the combination of these two herbicides distinctly increased N₂O and CH₄ emissions. Cumulative N₂O emissions (kg N₂O-N) followed the order of bensulfuron methyl (0.35 kg ha⁻¹) < pretilachlor (0.36 kg ha⁻¹) < control (0.45 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (0.49 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (0.54 kg ha⁻¹). Cumulative CH₄ emissions (kg CH₄), on the other hand, followed the order of bensulfuron methyl (47.89 kg ha⁻¹) < pretilachlor (73.17 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (93.50 kg ha⁻¹) < control (106.54 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (124.67 kg ha⁻¹). The inhibitory effect of separate application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% on N₂O emission was linked to lower mineral N, lower denitrifying and nitrifying activity and low denitrifier and nitrifier populations. Inhibitory effect on CH₄ emission, on the contrary, was linked to prevention in the drop of redox potential, lower readily mineralizable carbon (RMC) and microbial biomass carbon (MBC) contents as well as lower methanogenic and higher methanotrophic bacterial population. Admittedly, stimulatory effect of combined application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% at double dose on N₂O and CH₄ emission was related to reversal of the identified indicators of inhibition. Results indicate that while individual application of herbicides bensulfuron methyl 0.6% or pretilachlor 6.0% can reduce N₂O and CH₄ emission from flooded soil planted to rice, their combined application at normal dose can keep the emission at a comparatively lower level with significantly higher grain yield as compared to the herbicides applied alone.     

The use of anthracene as a model compound in a comparative study of hydrous pyrolysis methods for industrial waste remediation

Polycyclic aromatic hydrocarbons are very stable compounds and tend to bioaccumulate in the environment due to their high degree of conjugation and aromaticity. Hydrous pyrolysis is explored as a technique for the treatment of industrial water containing PAH, using anthracene as a model compound. The reactivity of anthracene under a range of temperatures and durations are studied in this paper. Aliquots of 1.0-10.0 mg of anthracene in a range of 1.0-5.0 mL of H₂O are subjected to hydrous pyrolysis under varied conditions of temperature, reagents and duration. The conditions include oxidising systems comprising distilled water, hydrogen peroxide and Nafion-SiO₂ solid catalyst in water; and reducing systems of formic acid and formic acid/Nafion-SiO₂/Pd-C catalysts to assess a range of redox reaction conditions. Oxygen in air played a role in some of the reaction conditions. Pyrolysed products were identified and quantified by the use of Gas Chromatography-Mass Spectrometry (GC-MS). The major products were anthrone, anthraquinone, xanthone from oxidation; and multiple hydro-anthracene derivatives from reductive hydogenation. The nature of reaction conditions influenced the extent of anthracene degradation. The products formed are more reactive (less stable) as compared to anthracene the starting material and will therefore be less persistent in the environment.     

Spatial distribution of organochlorine contaminants in soil, sediment, and fish in Bikini and Enewetak Atolls of the Marshall Islands, Pacific Ocean

Several nuclear tests were performed at Enewetak and Bikini Atolls in the Marshall Islands between 1946 and 1958. The events at Bikini Atoll involved several ships that were tested for durability during nuclear explosions, and 24 vessels now rest on the bottom of the Bikini lagoon. Nine soil samples were collected from different areas on the two islands of the atoll, and eighteen sediment, nine fish, and one lobster were collected in the vicinity of the sunken ships. Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polychlorinated terphenyls (PCTs) in these samples were analyzed using gas chromatography/ion trap mass spectrometry (GC/ITMS). The average recoveries ranged from 78% to 104% for the different PCB congeners. The limits of detection (LOD) for PCBs, PCTs, DDE, DDT, and dieldrin ranged 10-50 pg g⁻¹. Some fish from Enewetak contained PCBs at a concentration range of 37-137 ng g⁻¹, dry weight (dw), and most of the soils from Enewetak showed evidence of PCBs (22-392 ng g⁻¹ dw). Most of the Bikini lagoon sediment samples contained PCBs, and the highest was the one collected from around the Saratoga, an aircraft carrier (1555 ng g⁻¹ dw). Some of the fish samples, most of the soil samples, and only one of the sediment samples contained 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (DDE) and PCBs. In addition to PCBs, the soils from Enewetak Atoll contained PCTs. PCTs were not detected in the sediment samples from Bikini Atoll. The results suggest local pollution sources of PCBs, PCTs, and OCPs.     

Phenol depletion by thermally activated peroxydisulfate at 70°C

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70 °C from contaminated waters is investigated. Phenol in concentrations of 10⁻⁴ to 5 × 10⁻⁴ M is quantitatively depleted by 5 × 10⁻³ to 10⁻² M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70 °C does not lead to the mineralization of phenol. Thus PS activation at 70 °C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.     

Effects of benzo[a]pyrene as an environmental pollutant and two natural antioxidants on biomarkers of reproductive dysfunction in male rats

Benzo[a]pyrene (B[a]P) is an environmental toxicant and endocrine disruptor. Therefore, the aim of the present study was to investigate the toxicity of B[a]P in testis of rats and also to study the role of silymarin and thymoquinone (TQ) as natural antioxidants in the alleviation of such toxicity. Data of the present study showed that levels of testosterone, estrogen and progesterone were significantly decreased after treatment of rats with B[a]P. In addition, B[a]P caused downregulation of the expressions of steroidogenic enzymes including CYP17A1 and CP19A1, and decreased the activity of 17-β hydroxysteroid dehydrogenase (17β-HSD). Moreover, B[a]P decreased the activities of antioxidant enzymes including catalase (CAT), glutathione peroxidase (GP_X) and superoxide dismutase (SOD), and significantly increased free radicals levels in testis of male rats. However, pretreatment of rats with silymarin prior to administration of B[a]P was found to restore the level of free radicals, antioxidant status, and activities of steroidogenic enzymes to their normal levels in testicular tissues. Moreover, histopathological finding showed that silymarin recovered the abnormalities occurred in tubules caused by B[a] P in testis of rats. On the other hand, TQ showed pro-oxidant effects and did not ameliorate the toxic effects of B[a] P on the testicular tissue since it decreased antioxidant enzymes activities and inhibited the protein expression of CYP11A1 and CYP21A2 compared to control rats. Moreover, TQ decreased the levels of testosterone, estrogen, and progesterone either in the presence or absence of B[a]P. It is concluded that B[a]P decreased testosterone levels, inhibited antioxidant enzymes activities, caused downregulation of CYP isozymes involved in steroidogenesis, and increased free radical levels in testis. Moreover, silymarin was more effective than TQ in restoring organism health and alleviating the deleterious effects caused by B[a]P in the testis of rats. Due to its negative impact, it is highly recommended to limit the use of TQ as a dietary supplement since millions of people in the Middle East are using it to improve their health.

     

Comparison between UVA- and zero-valent iron-activated persulfate processes for degrading propylparaben

Conventional wastewater treatments are not efficient in removing parabens, which may thus end up in surface waters, posing a threat to aquatic biota and hu     

Enrichment of trace elements in the clay size fraction of mining soils

Reactive waste dumps with sulfide minerals promote acid mine drainage (AMD), which results in water and soil contamination by metals and metalloids. In these systems, contamination is regulated by many factors, such as mineralogical composition of soil and the presence of sorption sites on specific mineral phases. So, the present study dedicates itself to understanding the distribution of trace elements in different size fractions (<2-mm and <2-μm fractions) of mining soils and to evaluate the relationship between chemical and mineralogical composition. Cerdeirinha and Penedono, located in Portugal, were the waste dumps under study. The results revealed that the two waste dumps have high degree of contamination by metals and arsenic and that these elements are concentrated in the clay size fraction. Hence, the higher degree of contamination by toxic elements, especially arsenic in Penedono as well as the role of clay minerals, jarosite, and goethite in retaining trace elements has management implications. Such information must be carefully thought in the rehabilitation projects to be planned for both waste dumps.     

Benthic ecosystem functioning in the severely contaminated Mar Piccolo of Taranto (Ionian Sea,Italy): focus on heterotrophic pathways

The benthic ecosystem functioning is a rarely applied holistic approach that integrates the main chemical and biological features of the benthic domain with the key processes responsible for the flux of energy and C through the system. For the first time, such conceptual model, with an emphasis on the heterotrophic pathways, has been applied to the sediments at four stations within one of the most polluted coastal areas in Italy: the Mar Piccolo of Taranto. The functioning of the benthic ecosystem was different according to the investigated site. Nearby the military arsenal, i.e., the main source of organic contaminants and heavy metals, the system seemed inhibited at all the investigated structural and functional levels. Slow microbial processes of C reworking together with very limited densities of benthic fauna suggested a modest transfer of C both into a solid microbial loop and to the higher trophic levels. On the other hand, the ingression of marine water through the “Navigabile” channel seemed to stimulate the organic matter degradation and, consequently, the proliferation of meiofauna and macrofauna. In the innermost part of the basin, the system functioning, to some extent, is less impacted by contaminants and more influenced by mussel farms. The organic matter produced by these bivalves fueled faster C reworking by benthic prokaryotes and enhanced the proliferation of filter feeders.