Removal of heavy metal ions from wastewaters using dendrimer-functionalized multi-walled carbon nanotubes

Dendrimer-functionalized multi-walled carbon nanotubes (MWCNT) for heavy metal ion removal from wastewaters were developed. Triazole dendrimers (TD) were built directly onto the carbon nanotube surface by successive click chemistry reactions affording the zero- and first-generation dendrimer-functionalized MWCNT (MWCNT-TD1 and MWCNT-TD2). The Moedritzer-Irani reaction carried out on the amino groups present on the MWCNT-TD2 sample gave the corresponding α-aminophosphonate nanosystem MWCNT-TD2P. Both MWCNT-TD2 and MWCNT-TD2P nanosystems have been characterized by physical, chemical, and morphological analyses. Their chelating abilities towards the toxic metal ions Pb²⁺, Hg²⁺, and Ni²⁺ and the harmless Ca²⁺ ion have been experimentally evaluated in the two different sets of experiments and at the salt concentrations of 1 mg/mL or 1 μg/mL by inductively coupled plasma mass spectrometry (ICP-MS). The results of these studies pointed out the interesting chelating behavior for the phosphonated nanosystem towards the Hg²⁺ ion. The complexation mode of the best chelating system MWCNT-TD2P with mercury was investigated through density functional theory (DFT) calculations, suggesting a chelation mechanism involving the two oxygen atoms of the phosphate group. The synthesized dendrimers, supported on the multi-walled carbon nanotubes, have shown the potential to be used for the selective toxic metal ion removal and recovery.     

Performance evaluation of two protective treatments on salt-laden limestones and marble after natural and artificial weathering

Salt crystallization is a major damage factor in stone weathering, and the application of inappropriate protective products may amplify its effects. This research focuses on the evaluation of two protective products' performance (organic polydimethylsiloxane and inorganic ammonium oxalate (NH₄)₂(COO)₂·H₂O) in the case of a salt load from behind. Experimental laboratory simulations based on salt crystallization cycles and natural weathering in an urban area were carried out. The effects were monitored over time, applying different methods: weight loss evaluation, colorimetric and water absorption by capillarity measurements, stereomicroscope observations, FTIR and SEM-EDS analyses. The results showed minor impact exerted on the short term on stones, particularly those treated with the water repellent, by atmospheric agents compared to salt crystallization. Lithotypes with low salt load (Gioia marble) underwent minor changes than the heavily salt-laden limestones (Lecce and Ançã stones), which were dramatically damaged when treated with polysiloxane. The results suggest that the ammonium oxalate treatment should be preferred to polysiloxane in the presence of soluble salts, even after desalination procedures which might not completely remove them. In addition, the neo-formed calcium oxalate seemed to effectively protect the stone, improving its resistance against salt crystallization without occluding the pores and limiting the superficial erosion caused by atmospheric agents.     

Is Urban Stream Restoration Worth It?1

Kenney, Melissa A., Peter R. Wilcock, Benjamin F. Hobbs, Nicholas E. Flores, and Daniela C. Martínez, 2012. Is Urban Stream Restoration Worth It? Journal of the American Water Resources Association (JAWRA) 48(3): 603-615. DOI: 10.1111/j.1752-1688.2011.00635.x Abstract: Public investment in urban stream restoration is growing, yet little has been done to quantify whether its benefits outweigh its cost. The most common drivers of urban stream projects are water quality improvement and infrastructure protection, although recreational and aesthetic benefits are often important community goals. We use standard economic methods to show that these contributions of restoration can be quantified and compared to costs. The approach is demonstrated with a case study in Baltimore, Maryland, a city with a legal mandate to reduce its pollutant load. Typical urban stream restoration costs of US$500-1,200 per foot are larger than the cost of the least expensive alternatives for management of nitrogen loads from stormwater (here, detention ponds, equivalent to $30-120 per foot of restored stream) and for protecting infrastructure (rip-rap armoring of streambanks, at $0-120 per foot). However, the higher costs of stream restoration can in some cases be justified by its aesthetic and recreational benefits, valued using a contingent valuation survey at $560-1,100 per foot. We do not intend to provide a definitive answer regarding the worth of stream restoration, but demonstrate that questions of worth can be asked and answered. Broader application of economic analysis would provide a defensible basis for understanding restoration benefits and for making restoration decisions.     

Fukushima fallout in Northwest German environmental media

Traces of short- and long-lived fallout isotopes (¹³¹I, ¹³⁴Cs and ¹³⁷Cs) were found in environmental samples collected in Northwest Germany (rain water, river sediment, soil, grass and cow milk) from March to May 2011, following the radioactivity releases after the nuclear accident in Fukushima, Japan. The measured concentrations are consistent with reported concentrations in air, amount of rainfall and expected values applying simple radioecological models. The [¹³⁴Cs]/[¹³⁷Cs] ratio reported for air (about 1) allows for discrimination between “recent” and “old” ¹³⁷Cs. Expected ¹³⁶Cs values fell below the detection limits of the instrumentation, despite large sample masses and long counting times.     

Impact of water quality on bacterioplankton assemblage along Cértima River Basin (central western Portugal) assessed by PCR–DGGE and multivariate analysis

The information on bacterial community composition (BCC) in Portuguese water bodies is very scarce. Cértima River (central western Portugal) is known to have high levels of pollution, namely organic. In the present work, the BCC from a set of 16 water samples collected from Cértima River Basin and its main tributaries was characterized using 16S rDNA–denaturing gradient gel electrophoresis, a culture-independent molecular approach. Molecular data were related to environmental parameters through multivariate analysis to investigate potential impact of water pollution along the river. Principal component analysis using environmental data showed a water quality gradient from more pristine waters (at the mountain tributaries) to waters with increasingly eutrophic potential (such as Fermentelos Lake). This gradient was mainly defined by factors such as organic and inorganic nutrient sources, electrical conductivity, hydrogen carbonate concentration, and pH. Molecular results showed variations in BCC along Cértima River Basin but in the main river section, a Bacteroidetes phylotype (Flavobacterium sp.) proved to be dominant throughout the river course. Multivariate analysis suggests that spatial variation of BCC along the Cértima River Basin depended mainly on parameters such as Chl a, total suspended solid (TSS), total organic carbon, electrical conductivity, and HCO _boxclose^-_{3}^{-} levels. Bacteroidetes phylotypes were all related to higher electrical conductivity and HCO₃^-_{3}^{-} levels although some of these were also correlated with high SO₄^2-_{4}^{2-} and others with high soluble reactive phosphorus, nitrate, TN, and Kjeld-N levels. The Gammaproteobacteria occurrence was correlated with high SO₄^2-_{4}^{2-} levels. One of the Betaproteobacteria phylotypes showed to correlate with low redox potential (E_h) and high temperature, pH, TSS, and Chl a levels while another one showed a negative correlation with Chl a values.     

A correlation between the fate and non-extractable residue formation of 14C-metalaxyl and enzymatic activities in soil

Extracellular, oxidative soil enzymes like monophenol oxidases and peroxidases play an important role in transformation of xenobiotics and the formation of organic matter in soil. Additionally, these enzymes may be involved in the formation of non-extractable residues (NERs) of xenobiotics during humification processes. To examine this correlation, the fate of the fungicide ¹⁴C metalaxyl in soil samples from Ultuna (Sweden) was studied. Using different soil sterilization techniques, it was possible to differentiate between free, immobilized, and abiotic (“pseudoenzyme”-like) oxidative activities. A correlation between the formation of metalaxyl NER and soil organic matter content, biotic activities, as well as extracellular phenoloxidase and peroxidase activities in the bulk soil and its particle size fractions was determined. Extracellular soil-bound enzymes were involved in NER formation (up to 8% of applied radioactivity after 92 days) of the fungicide independently from the presence of living microbes and different distributions of the NER in the soil humic subfractions.     

Waste collection in developing countries – Tackling occupational safety and health hazards at their source

Waste management procedures in developing countries are associated with occupational safety and health risks. Gastro-intestinal infections, respiratory and skin diseases as well as muscular-skeletal problems and cutting injuries are commonly found among waste workers around the globe. In order to find efficient, sustainable solutions to reduce occupational risks of waste workers, a methodological risk assessment has to be performed and counteractive measures have to be developed according to an internationally acknowledged hierarchy. From a case study in Addis Ababa, Ethiopia suggestions for the transferral of collected household waste into roadside containers are given. With construction of ramps to dump collected household waste straight into roadside containers and an adaptation of pushcarts and collection procedures, the risk is tackled at the source.     

The amorphous Zn biomineralization at Naracauli stream,Sardinia: electron microscopy and X-ray absorption spectroscopy

An amorphous Zn biomineralization (“white mud”), occurring at Naracauli stream, Sardinia, in association with cyanobacteria Leptolyngbya frigida and diatoms, was investigated by electron microscopy and X-ray absorption spectroscopy. Preliminary diffraction analysis shows that the precipitate sampled on Naracauli stream bed is mainly amorphous, with some peaks ascribable to quartz and phyllosilicates, plus few minor unattributed peaks. Scanning electron microscopy analysis shows that the white mud, precipitated in association with a seasonal biofilm, is made of sheaths rich in Zn, Si, and O, plus filaments likely made of organic matter. Transmission electron microscopy analysis shows that the sheaths are made of smaller units having a size in the range between 100 and 200 nm. X-ray absorption near-edge structure and extended X-ray absorption fine structure data collected at the Zn K-edge indicate that the biomineral has a local structure similar to hemimorphite, a zinc sorosilicate. The differences of this biomineral with respect to the hydrozincite biomineralization documented about 3 km upstream in the same Naracauli stream may be related to either variations in the physicochemical parameters and/or different metabolic behavior of the involved biota.