Itaconic Acid Grafted Starch Hydrogels as Metal Remover: Capacity,Selectivity and Adsorption Kinetics

Hydrogels were synthesized by free radical graft copolymerization of itaconic acid (IA) onto corn starch (S-g-IA). For this purpose, potassium permanganate (KMnO₄)-sodium bisulfite (NaHSO₃) was used as redox initiation system. The formation of grafted starches was confirmed by Fourier transform infrared spectroscopy, wide angle X-ray scattering, thermogravimetric analysis and scanning electron microscopy. The effect of monomer concentration, neutralization, addition of crosslinking agent, N,N-bismetilenacrilamide (MBAm), and initiator concentration on grafting efficiency and adsorption capacity of the starch hydrogels was investigated. It was demonstrated that the introduction of carboxyl and carbonyl groups promoted starch hydration and swelling. Grafting degree increased with the decrease of monomer concentration, increase of initiator concentration, grade of neutralization and the addition of MBAm without neutralization. Remarkably the resulting materials exhibited water absorption capacities between 258 and 1878% and the ability to adsorb metal ions. It was experimentally confirmed the metal uptake, obtaining the higher adsorption capacity (q _e  = 35 mg/g) for the product prepared with the pre-oxidation and lower initiator concentration. The removal capacity order was Pb²⁺>Ni²⁺>Zn²⁺>Cd²⁺. Moreover, the experimental kinetic and the equilibrium adsorption data for Ni²⁺ and Pb²⁺ were best fitted to the pseudo-second order and Freundlich isotherm models, respectively. This work describes for the first time the preparation of metal removal hydrogels based on starch and itaconic acid using the pair redox system KMnO₄/NaHSO₃, which avoids the starch hydrolysis and allows itaconic acid grafting incorporation without the requirement of more reactive comonomers.     

Monitoring the photochemical degradation of triclosan in wastewater by UV light and sunlight using solid-phase microextraction

Photo solid-phase microextraction (photo-SPME) is applied for the first time to study the photochemical behavior of an emerging pollutant, triclosan, in real contaminated wastewater samples using a solar simulator. In this study, water samples are extracted by SPME and then, the fiber coating is irradiated for a selected time. This on-fiber procedure, so-called photo-SPME, followed by gas chromatography-mass spectrometry makes it possible to study photodegradation kinetics and the generation of byproducts. Several photoproducts were identified in the real samples including the 2,8-dichlorodibenzo-p-dioxin, dichlorophenols and a compound tentatively identified as other DCDD congener or a dichlorohydroxydibenzofuran. Accordingly, it was possible to postulate main photodegradation mechanisms. Photo-SPME demonstrated slower kinetics in wastewater than in spiked ultrapure water probably due to the presence of dissolved organic matter. This technique was extensively compared with conventional aqueous photodegradation showing high similarity. The influence of pH on the triclosan photolysis and on the triclosan-dioxin conversion was also investigated in wastewater. Photodegradation of triclosan and formation of 2,8-DCDD occurred independently of sample pH. This study represents an advance in the use of photo-SPME to understand the photochemical fate of environmental organic pollutants and demonstrates its clear advantages with real samples.     

Patterns of soil contamination,erosion and river loading of metals in a gold mining region of northern Mongolia

Mining has become one of the main causes of increased heavy metal loading of river systems throughout the world. There is however an evident gap between assessments of soil contamination and metal release at the mined sites and estimates of river pollution. The present work focuses on Zaamar Goldfield, which is one of the largest placer gold mines in the world, located along the Tuul River, Mongolia, which ultimately drains into Lake Baikal, Russia. It combines field observations in the river basin with soil erosion modelling and aims at quantifying the contribution from natural erosion of metal-rich soil to observed increases in mass flows of metals along the Tuul River. Results show that the sediment delivery from the mining area to the Tuul River is considerably higher than the possible contribution from natural soil erosion. This is primarily due to excessive mining-related water use creating turbid wastewaters, disturbed filtering functions of deposition areas (natural sediment traps) close to the river and disturbances from infrastructures such as roads. Furthermore, relative to background levels, soils within Zaamar Goldfield contained elevated concentrations of As, Sr, Mn,V, Ni, Cu and Cr. The enhanced soil loss caused by mining-related activities can also explain observed, considerable increases in mass flows of metals in the Tuul River. The present example from Tuul River may provide useful new insights regarding the erosion and geomorphic evolution of mined areas, as well as the associated delivery of metals into stream networks.

     

Estimates of (239+240)Pu inventories in Gdańsk Bay and Gdańsk basin

This paper presents and discusses the results of (239+240)Pu determinations in different components of Gdańsk bay and Gdańsk basin ecosystem, as well as estimated sources and inventories of plutonium in these basins. The total plutonium (239+240)Pu activities deposited in Gdańsk bay and Gdańsk basin sediments are 1.18 TBq and 3.77 TBq, respectively. Two rivers, the Vistula and Neman rivers, and atmospheric fallout were distinguished as the main sources of plutonium in these basins. In seawater (with suspended matter included) there is about 2.33 GBq (239+240)Pu (0.2% of total activity) in Gdańsk bay and 9.92 GBq (239+240)Pu (0.3% of total activity) in Gdańsk basin. In both cases, 56% of (239+240)Pu is associated with suspended matter. Organisms contain 3.81 MBq in Gdańsk bay and 7.45 MBq (239+240)Pu in Gdańsk basin. From this value in Gdańsk bay 82.1% of plutonium is associated with zoobenthos, 13.6% with phytobenthos, 1.6% with phytoplankton, 1.5% with zooplankton and 1.2% with fish. In Gdańsk basin, 83.2% is associated with zoobenthos, 7.5% with phytobenthos, 3.6% with phytoplankton, 3.2% with zooplankton and 2.5% with fish.     

The impact of inorganic tin on the planktonic cyanobacterium Synechocystis aquatilis: the effect of pH and humic acid

The influence of inorganic tin compounds on the unicellular cyanobacterium Synechocystis aquatilis was studied, and its dependence on changing pH of the surrounding medium and the presence of humic acid. Both Sn(II) and Sn(IV), used as chlorides (at the concentrations 1-10 mg litre(-1)), inhibit the growth and chlorophyll a content of the cyanobacterium cultures, but only under alkaline conditions. Generally, the observed tin toxicity increased with increase of metal concentration, time of exposure and pH value of the medium (in the range 7-9.8). Sn(II) seems to be more toxic than Sn(IV). At the lowest studied metal concentration (1 mg litre(-1)), Sn(II) caused a 36 and 40% decrease in growth and chl a content, respectively, after 96 h exposure at pH 9.8, while Sn(IV) caused even a slight increase of both physiological parameters (hormetic effect). Similar increases in growth and chl a content were also observed at a high Sn (II) and Sn(IV) concentration (10 mg litre(-1)), but only in cultures exposed to metal at pH 7. At high pH (9.8), 10 mg litre(-1) of Sn(II) and Sn(IV) significantly suppressed both the growth of the cyanobacterium (by 54.2 and 26.1%, respectively) and the chl a content in cultures (by 58.2 and 24%, respectively). Humic acid reduced the toxicity of tin towards the cyanobacterium. The observed effects of pH and complexing ligand on the inorganic tin toxicity are discussed in the context of changing, chemical metal speciation and bioavailability.     

Exploring Patterns of Seafood Provision Revealed in the Global Ocean Health Index

Sustainable provision of seafood from wild-capture fisheries and mariculture is a fundamental component of healthy marine ecosystems and a major component of the Ocean Health Index. Here we critically review the food provision model of the Ocean Health Index, and explore the implications of knowledge gaps, scale of analysis, choice of reference points, measures of sustainability, and quality of input data. Global patterns for fisheries are positively related to human development and latitude, whereas patterns for mariculture are most closely associated with economic importance of seafood. Sensitivity analyses show that scores are robust to several model assumptions, but highly sensitive to choice of reference points and, for fisheries, extent of time series available to estimate landings. We show how results for sustainable seafood may be interpreted and used, and we evaluate which modifications show the greatest potential for improvements.     

Sublethal toxicity of the Prestige oil spill on yellow-legged gulls

The Prestige oil spill in November 2002 is considered the biggest large-scale catastrophe of its type in Europe, thousands of seabirds dying in the subsequent months. Here, the total concentration of 16 polycyclic aromatic hydrocarbons (TPAH) was measured in the blood cell fraction of adult and chick yellow-legged gulls (Larus michahellis) from unoiled and oiled coastal areas in North Western Spain. In addition, hematocrit, plasma metabolites, electrolytes and enzymes, as well as body mass were determined in the same individuals. Our results strongly suggest the presence of health damages of sublethal nature in adult gulls breeding in oiled colonies 17 months after the Prestige oil spill. This is supported by the following evidences: (1) gulls sampled in unoiled and oiled colonies differed in blood TPAH levels, (2) gulls sampled in unoiled and oiled colonies differed in several blood parameters indicative of physiological disorders, and (3) TPAH in blood was significantly related to several of these parameters. Differences in the level of asparatate aminotransferase (AST), gamma-glutamyl transferase (GGT), total protein, glucose and inorganic phosphorus suggest damages on some vital organs (i.e. liver and kidney) in adult birds from oiled areas. Meanwhile, chicks presented weaker effects than adults, showing only between-area differences in hematocrit. Since TPAH levels in blood did not differ between both age-groups, the stronger effects on adults should be due to their longer exposure to these pollutants and/or to severe exposure in the months following the spill. The presence of PAHs in chicks indicates that these pollutants were incorporated into the food chain because nestlings would have been only exposed to contaminated organisms in the diet (e.g. fishes and crustaceans). Our findings support the view that PAHs may deeply alter the physiology of seabirds, and emphasize the necessity of quantifying the circulating levels of these compounds in order to evaluate the sublethal effects associated to large oil spills.     

Exposure to heavy metals and PCDD/Fs by the population living in the vicinity of a hazardous waste landfill in Catalonia, Spain: Health risk assessment

Most fly ashes produced in municipal waste incinerators of Catalonia (Spain) are deposited in a hazardous waste landfill (HWL) placed in Castellolí (Barcelona). This facility means a concern for the population living nearby. In response to this, we performed a probabilistic study focused on assessing human health risks derived from environmental exposure to heavy metals and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) around the HWL. Concentrations of various metals and PCDD/Fs were determined in soil and air samples collected at the HWL, and in 4 locations around it. Health risks were evaluated according to the distance from the sampling locations to the HWL (near and far-sites). In general terms, metal and PCCD/F levels were relatively low in air and soil samples. However, concentrations of PCDD/Fs, as well as those of some metals, were found to be relatively higher in the HWL and Castellolí (the nearest village) samples than in those collected far away, resulting in a slight increase of exposure to those pollutants. Anyhow, the current concentrations of metals and PCDD/Fs suggest that it is highly unlikely that there are any additional non-carcinogenic and carcinogenic risks for the population living near the HWL.