Water Remediation: PVA-Based Magnetic Gels as Efficient Devices to Heavy Metal Removal

Scientific and technological researches are devoted to obtain materials capable of retaining different kinds of pollutants, contributing to contamination solutions. In this context, hydrogels have emerged as great candidates because of their excellent absorption properties as well as good mechanical, thermal and chemical properties. More specifically, ferrogels (magnetic gels) present the extra advantage of being easily manipulated by a permanent magnet. Here, we present the results derived from the application of ferrogels as efficient tools to extract heavy metal pollutants from wastewater samples. The gels were prepared following the method of freezing and thawing of a polyvinyl alcohol aqueous solution with magnetic nanoparticles coated with polyacrylic acid. Ferrogels were fully characterized and their ability to retain Cu²⁺ and Cd²⁺, as model heavy metals, was studied. Thus kinetics and mechanisms of adsorption were evaluated and modeled. The concentration of MNPs on the PVA matrix was key to improve the adsorption capability (approximately the double of retention is improved by the MNPs addition). The adsorption kinetics was determined as pseudo-second order model, whereas the Langmuir model was the most appropriate to explain the behavior of the gels. Finally reuse ability was evaluated to determine the real potential of these materials, the ferrogels demonstrated high efficiency up to about five cycles, retaining about 80–90% of their initial adsorption capability. All the results indicated that the materials are promising candidates able to compete with the commercial technology regarding to water remediation.     

Daily ingestion of 232Th, 238U, 226Ra, 228Ra and 210Pb in vegetables by inhabitants of Rio de Janeiro City

The concentrations of the naturally occurring radionuclides 232Th, 238U, 210Pb, 226Ra and 238Ra were determined in the vegetables (leafy vegetables, fruit, root, bean and rice) and derived products (sugar, coffee, manioc flour, wheat flour, corn flour and pasta) consumed most by the adult inhabitants of Rio de Janeiro City. A total of 88 samples from 26 different vegetables and derived products were analyzed. The highest contribution to radionuclide intake arises from bean, wheat flour, manioc flour, carrot, rice, tomato and potato consumption. The estimated daily intakes due to the consumption of vegetables and derived products are 1.9 mBq of 232Th (0.47 microg), 2.0 mBq of 238U (0.17 microg), 19 mBq of 236Ra, 26 mBq of 210Pb and 47 mBq of 228Ra. The estimated annual effective dose due to the ingestion of vegetables and their derived products with the long-lived natural radionuclides is 14.5 microSv. Taking into account literature data for water and milk from Rio de Janeiro the dose value increases to 29 microSv, with vegetables and derived products responsible for 50% of the dose and water for 48%. 210Pb (62%) and 228Ra (24%) were found to be the main sources for internal irradiation.     

Biomagnification of anthropogenic and naturally-produced organobrominated compounds in a marine food web from Sydney Harbour, Australia

Polybrominated diphenyl ethers (PBDEs) and naturally-produced organobrominated compounds, such as methoxylated PBDEs (MeO-PBDEs), have been scarcely studied in the Southern Hemisphere. Yet, sources of the latter group of compounds were found in Southern regions, specifically in Australia. The environmental distribution and biomagnification potential of organobrominated compounds were therefore investigated in a representative aquatic food chain (invertebrates and fish) from the Sydney Harbour, Australia. Mean PBDE concentrations ranged from 6.4 ng/g lipid weight (lw) in squid to 115 ng/g lw in flounder. BDE 47 was the dominant congener, followed by BDE 100. Mean levels of MeO-PBDEs (sum of congeners 2’-MeO-BDE 68 and 6-MeO-BDE 47) were as high as 110 ng/g lw in tailor, with a slight dominance of 2’-MeO-BDE 68. Polybrominated hexahydroxanthene derivates (PBHDs), another class of naturally-produced compounds, were found at variable concentrations and ranged from 4.7 ng/g lw in fanbelly and 146 ng/g lw in tailor. The tribrominated PBHD isomer dominated in the samples, except for luderick and squid. The lower levels of PBDEs found in luderick from the harbour compared to those obtained from the upper Parramatta River indicated a terrestrial (anthropogenic) origin of PBDEs, while the higher levels of MeO-PBDEs and PBHDs in the samples from the harbour confirmed the marine (natural) origin of these compounds. The highest trophic magnification factor (TMF) was found for sum PBDEs (3.9), while TMFs for sum MeO-PBDEs and sum PBHDs were 2.9 and 3.4, respectively. This suggests that biomagnification occurs in the studied aquatic food chain for anthropogenic brominated compounds, but also for the naturally-produced organobromines.     

Biomagnification of naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) in harbour seals and harbour porpoises from the Southern North Sea

Harbour seals and harbour porpoises are top predator species from the North Sea, have long life spans and hence, are known to accumulate high levels of anthropogenic contaminants. To gain knowledge about the behaviour of naturally-produced compounds in these marine mammals, the biomagnification of naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) was assessed. The biomagnification of MeO-PBDEs (2′-MeO-BDE 68 and 6-MeO-BDE 47) was lower in harbour seals (all biomagnification factors (BMFs) < 1) compared to the same age–gender groups of the harbour porpoises (all BMFs > 1). This may indicate a better metabolic breakdown of MeO-PBDEs in harbour seals, as was previously suggested for polybrominated diphenyl ethers (PBDEs). In both predators, 6-MeO-BDE 47 had the highest concentrations (range: 45–483 ng/g lw and 2–38 ng/g lw for harbour porpoises and seals, respectively) compared to 2′-MeO-BDE 68 (range: 2–28 ng/g lw and 1–6 ng/g lw for harbour porpoises and seals, respectively). In general, the highest concentrations were found in juveniles, suggesting an increased biotransformation capacity with age or the influence of dilution by growth for both species. Here we show that naturally-produced brominated organic compounds can biomagnify and accumulate in North Sea top predators, although to a lesser extent than anthropogenic lipophilic contaminants, such as polychlorinated biphenyls (PCBs) or PBDEs.     

Organochlorine and heavy metals in newborns: Results from the Flemish Environment and Health Survey (FLEHS 2002–2006)

To collect regional information on internal levels of pollutants in humans in Flanders, 1196 mother–child pairs were systematically recruited in 2002–2003 via 25 maternities across Flanders. Cd, Pb, PCB congeners 118, 170, 138, 153 and 180, p,p′-DDE — a key metabolite of DDT- and hexachlorobenzene (HCB) were measured in cord blood or plasma. Cd was detected in 64% of the samples (geometric mean 0.21 µg/L cord blood). p,p′-DDE (110 ng/g plasma lipids) and Pb (14.7 µg/L blood), were measurable in nearly all samples. The individual PCB congeners could be detected in 40 to 81% of the newborns (138 + 153 + 180 = 64.4 ng/g plasma lipids). HCB (18.9 ng/g plasma lipids) and dioxin-like compounds measured by DR-CALUX® (23 pg CALUX-TEQ/g lipids) were above detection limit in more than 75% of the samples. Age and smoking habits of the mothers, did not influence the cord blood Pb and Cd levels. The organochlorines increased 4 to 9% per year of the mother's age (partial R² = 0.05 to 0.22). Mothers had 2.6% less PCBs in cord blood (partial R² = 0.02) for each unit increase in pre-pregnancy BMI. Season of delivery, breastfeeding previous children or consumption of local dairy products, were minor determinants. Up to 20% of the variability in organochlorine concentrations was explained by residence area. It was concluded that the place of birth in Flanders is an important determinant of the load of pollutants measured at the start of life. This underlines the validity of human biomonitoring on (relatively) small geographical scale.     

Microsatellite data reveal fine genetic structure in male Guiana dolphins (<Emphasis Type="Italic">Sotalia guianesis)</Emphasis> in two geographically close embayments at south-eastern coast of Brazil

A large macrogeographic differentiation has been observed among Sotalia guianensis populations along the South American coast. However, no genetic structure has been detected so far in closely distributed populations of this species, even though it has been observed in other cetaceans. Here, we examined the fine scale population structure for the largest populations of S. guianensis inhabiting Sepetiba and Paraty embayments at the south-eastern coast of Rio de Janeiro, Brazil. Analysis of mitochondrial DNA (mtDNA) control region sequences failed to detect variability among sequences. Conversely, evidence of significant male population structure was found on the basis of ten nuclear microsatellite loci. Surprisingly, the microsatellite markers were able to distinguish between individuals from the two embayments located 60 km apart. The results suggest that differences in habitat type and behavioral specializations are likely to explain the patterns of genetic structure. These findings should provide baselines for the management of communities exposed to increasing human-driven habitat loss.     

Scale-dependent response diversity of seabirds to prey in the North Sea

Functional response diversity is defined as the diversity of responses to environmental change among species that contribute to the same ecosystem function. Because different ecological processes dominate on different spatial and temporal scales, response diversity is likely to be scale dependent. Using three extensive data sets on seabirds, pelagic fish, and zooplankton, we investigate the strength and diversity in the response of seabirds to prey in the North Sea over three scales of ecological organization. Two-stage analyses were used to partition the variance in the abundance of predators and prey among the different scales of investigation: variation from year to year, variation among habitats, and variation on the local patch scale. On the year-to-year scale, we found a strong and synchronous response of seabirds to the abundance of prey, resulting in low response diversity. Conversely, as different seabird species were found in habitats dominated by different prey species, we found a high diversity in the response of seabirds to prey on the habitat scale. Finally, on the local patch scale, seabirds were organized in multispecies patches. These patches were weakly associated with patches of prey, resulting in a weak response strength and a low response diversity. We suggest that ecological similarities among seabird species resulted in low response diversity on the year-to-year scale. On the habitat scale, we suggest that high response diversity was due to interspecific competition and niche segregation among seabird species. On the local patch scale, we suggest that facilitation with respect to the detection and accessibility of prey patches resulted in overlapping distribution of seabirds but weak associations with prey. The observed scale dependencies in response strength and diversity have implications for how the seabird community will respond to different environmental disturbances.     

Acid Rain in Downtown São Paulo City, Brazil

During the period from July 2002 to June 2004, the chemical characteristics of the rainwater samples collected in downtown São Paulo were investigated. The analysis of 224 wet-only precipitation samples included pH and electrical conductivity, as well as major ions (Na⁺, $ \rm NH^{ + }_{4} During the period from July 2002 to June 2004, the chemical characteristics of the rainwater samples collected in downtown S?o Paulo were investigated. The analysis of 224 wet-only precipitation samples included pH and electrical conductivity, as well as major ions (Na⁺, , K⁺, Ca²⁺, Mg²⁺, Cl⁻, , ) and carboxylic acids (acetic, formic and oxalic) using ion chromatography. The volume weighted mean, VWM, of the anions , and Cl⁻ was, respectively, 20.3, 12.1 and 10.7 μmol l⁻¹. Rainwater in S?o Paulo was acidic, with 55% of the samples exhibiting a pH below 5.6. The VWM of the free H⁺ was 6.27 μmol l⁻¹), corresponding to a pH of 5.20. Ammonia (NH₃), determined as (VWM = 32.8 μmol l⁻¹), was the main acidity neutralizing agent. Considering that the H⁺ ion is the only counter ion produced from the non-sea-salt fraction of the dissociated anions, the contribution of each anion to the free acidity potential has the following profile: (31.1%), (26.0%), CH₃COO⁻ (22.0%), Cl⁻ (13.7%), HCOO⁻ (5.4%) and (1.8%). The precipitation chemistry showed seasonal differences, with higher concentrations of ammonium and calcium during autumn and winter (dry period). The marine contribution was not significant, while the direct vehicular emission showed to be relevant in the ionic composition of precipitation.     

One-Component Spray Polyurethane Foam from Liquefied Pinewood Polyols: Pursuing Eco-Friendly Materials

The use of petroleum-derived products should be avoided regarding the principles of green and sustainable chemistry. The work reported herein, is aimed at the liquefaction of pine shavings for the production of an environmentally-friendly polyol suitable to be used in the formulations of sprayable polyurethane foams. The biopolyols were obtained in high yield and were used to replace those derived from fossil sources, to produce more “greener” polyurethane foams and therefore, less dependent on petroleum sources, since the polyol component was substituted by products resulting from biomass liquefaction. The partial and fully exchange of the polyols was accomplished, and the results compared with a reference foam. The foams were afterward, chemical, physical, morphological, and mechanically characterized. The complete replacement of polyether polyol and polyol polyester has presented some similar characteristics as that used as a reference, validating that the path chosen for the development of more sustainable materials is on the right track for the contribution to a cleaner world.