Constructing herbicide metribuzin sustained-release formulations based on the natural polymer poly-3-hydroxybutyrate as a degradable matrix

Polymer poly(3-hydroxybutyrate) [P(3HB)] has been used as a matrix in slow-release formulations of the herbicide metribuzin (MET). Physical P(3HB)/MET mixtures in the form of solutions, powders, and emulsions were used to construct different metribuzin formulations (films, granules, pellets, and microparticles). SEM, X-Ray, and DSC proved the stability of these formulations incubated in sterile water in vitro for long periods of time (up to 49 days). Metribuzin release from the polymer matrix has been also studied. By varying the shape of formulations (microparticles, granules, films, and pellets), we were able to control the release time of metribuzin, increasing or decreasing it.     

Challenging established narratives on soil erosion and shifting cultivation in Laos

The official environmental discourse in Laos describes a “chain of degradation” stretching from upland shifting cultivation, increased runoff and soil erosion to the siltation of wetlands and reservoirs. This perspective has had wide‐ranging impacts on rural development policy which, in the uplands, has long favoured forest conservation over agriculture. Integrating soil erosion and water sediment data with local perceptions of land degradation in an upland village of northern Laos, this study tests the validity of the official environmental discourse. Biophysical measurements made in a small agricultural catchment indicate a significant correlation between the spatial extent of cultivation and soil erosion rates. However, sediment yields recorded at the outlet of the catchment highlight relatively low levels of off‐site sediment exportation. Furthermore, farmers' perceptions suggest that local land degradation issues and crop yield declines could be less related to soil erosion than to agricultural land shortage, increased weed competition, and fertility losses resulting from the intensification of shifting cultivation. The study concludes that a better understanding and management of land degradation issues can be achieved by developing more inclusive and scientifically‐informed approaches to environmental perceptions and narratives.     

Genotoxicity monitoring of freshwater environments using caged crayfish (Astacus leptodactylus)

Genotoxicity of freshwater pollution was assessed by measuring DNA damage in haemocytes of caged freshwater crayfish Astacus leptodactylus by the means of Comet assay and micronucleus test, integrated with the measurements of physiological (total protein concentration) and immunological (total haemocyte count) haemolymph parameters as biomarkers of undergone stress. Crayfish were collected at the reference site (River Mre?nica) and exposed in cages for 1 week at three polluted sites along the Sava River (Zagreb, Sisak, Krapje). The long term pollution status of these locations was confirmed by chemical analyses of sediments. Statistically significant increase in DNA damage measured by the Comet assay was observed at all three polluted sites comparing to the crayfish from reference site. In addition, native crayfish from the mildly polluted site (Krapje) cage-exposed on another polluted site (Zagreb) showed lower DNA damage than crayfish from the reference site exposed at the same location indicating adaptation and acclimatisation of crayfish to lower levels of pollution. Micronuclei induction showed similar gradient of DNA damage as Comet assay, but did not reach the statistical significance. Observed increase in total haemocyte count and total protein content in crayfish from polluted environments in the Sava River also confirmed stress caused by exposure to pollution. The results of this study have proved the applicability of caging exposure of freshwater crayfish A. leptodactylus in environmental genotoxicity monitoring using Comet assay and micronucleus test.     

Pd-Fe nanoparticles stabilized by chitosan derivatives for perchloroethene dechlorination

A series of chitosan-stabilized Pd-NZVI (nano-zero-valent-iron) catalysts for dechlorination with variation in their composition and in the nature of the polymer has been prepared. The synthesis procedures and palladium and chitosan contents were optimized. It was demonstrated by the XPS method that Fe and Pd in Fe-Pd/chitosan samples exist in the metallic state. The positive shift of the binding energy as compared with the bulk metal shows that the iron metal in the surface layers exists as very small nanoparticles. The prepared materials were characterized also by the XAS method. The presence of O and N atoms in the first coordination shell of the central Fe atom in the Fe-Pd/chitosan samples certifies the binding of the Fe metal particles with the chitosan surface via OH and NH(2) groups. The samples are characterized by the high stability of the nanoparticles as compared to unstabilized Pd-NZVI. The materials were tested to evaluate their catalytic activity in the perchloroethene (PCE) dechlorination reaction. Some samples of chitosan-stabilized Pd-NZVI revealed a good performance in PCE degradation as compared to unstabilized Pd-NZVI.     

Air pollution dispersion within urban street canyons

A semi-empirical mathematical model, Urban Street Model (USM), is proposed to efficiently estimate the dispersion of vehicular air pollution in cities. This model describes urban building arrangements by combining building density, building heights and the permeability of building arrangements relative to wind flow. To estimate the level of air pollution in the city of Krasnoyarsk (in Eastern Siberia), the spatial distribution of pollutant concentrations off roadways is calculated using Markov's processes in USM. The USM-predicted numerical results were compared with field measurements and with results obtained from other frequently used models, CALINE-4 and OSPM. USM consistently yielded the best results. OSPM usually overestimated pollutant concentration values. CALINE-4 consistently underestimated these values. For OSPM, the maximum differences were 160% and for CALINE-4 about 400%. Permeability and building density are necessary parameters for accurately modeling urban air pollution and influencing regulatory requirements for building planning.     

Organic carbon,total nitrogen,and water-soluble ions in clouds from a tropical montane cloud forest in Puerto Rico

Chemical characterization to determine the organic and nitrogen fractions was performed on cloud water samples collected in a mountaintop site in Puerto Rico. Cloud water samples showed average concentrations of 1.09 mg L^?1 of total organic carbon (TOC), of 0.85 mg L^?1 for dissolved organic carbon (DOC) and of and 1.25 mg L^?1 for total nitrogen (TN). Concentrations of organic nitrogen (ON) changed with the origin of the air mass. Changes in their concentrations were observed during periods under the influence of African dust (AD). The ON/TN ratios were 0.26 for the clean and 0.35 for the AD periods. Average concentrations of all these species were similar to those found in remote environments with no anthropogenic contribution. In the AD period, for cloud water the concentrations of TOC were 4 times higher and TN were 3 times higher than during periods of clean air masses associated with the trade winds. These results suggest that a significant fraction of TOC and TN in cloud and rainwater is associated to airborne particulate matter present in dust. Functional groups were identified using proton nuclear magnetic resonance (¹H NMR) spectroscopy. This characterization led to the conclusion that water-soluble organic compounds in these samples are mainly aliphatic oxygenated compounds, with a small amount of aromatics. The ion chromatography results showed that the ionic species were predominantly of marine origin, for air masses with and without African dust influence, with cloud water concentrations of NO₃^? and NH₄⁺ much lower than from polluted areas in the US. An increase of such species as SO₄^2?, Cl^?, Mg²⁺, K⁺ and Ca²⁺ was seen when air masses originated from northwest Africa. The changes in the chemical composition and physical properties of clouds associated with these different types of aerosol particles could affect on cloud formation and processes.     

Matrix effects on the de novo synthesis of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes

The formation of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes in de novo synthesis experiments have been studied on model fly ashes with a wide range of matrices. The model fly ash consisted of 18 selected matrices with the addition of CuCl(2) x 2H(2)O, activated charcoal and NaCl. The studied matrices were not restricted to the commonly investigated matrices with defined chemical composition (silica gel, alumina, florisil) and industrially produced adsorbents with silicate structures (diatomaceous earths), but also included natural occurring matrices (clays, kaolin, bentonite and feldspars). In addition fly ashes from a hazardous waste incinerator were included in the study for comparison. Differences in the isomer composition (homologue profiles and isomer patterns) of the substances formed by de novo synthesis experiments are discussed in dependence on the chemical composition of the studied matrices. The de novo synthesis experiments on matrices with silicate structures resulted in high concentration of mainly perchlorinated aromatic compounds while for other matrices in particular alkaline matrices a homologue shift to lower chlorinated homologues and lower formation rates were found. The paper discusses the resulting PCDD/PCDF pattern and compares them to the PCDD/PCDF profile found in naturally occurring kaolin and ball clay (illite).     

Cyanotoxin management and human health risk mitigation in recreational waters

The occurrence and severity of harmful cyanobacterial or blue-green algal blooms (HABs) have increased in recent decades, posing a serious threat of illness to humans. In some countries, water contaminated with cyanotoxins that is used for drinking or haemodialysis has posed a particularly serious risk. However, it is now recognized that recreational exposure to natural toxins by skin contact, accidental swallowing of water or inhalation can also cause a wide range of acute or chronic illnesses. In this review, we focus on the importance of cyanotoxin management in recreational waters. The symptoms related with HAB poisonings, the recommended safety concentrations limit for cyanobacteria and cyanotoxins in such waters, as well as early health hazard indicators of their presence and their monitoring are all discussed. We also present in this review an overview of the methods developed in recent decades for eliminating cyanobacteria and the toxic compounds that they produce.     

Application of multivariate statistical methods for groundwater physicochemical and biological quality assessment in the context of public health

Three representative areas (lowland, semi-mountainous, and coastal) have been selected for the collection of drinking water samples, and a total number of 28 physical, chemical, and biological parameters per water sample have been determined and analyzed. The mean values of the physical and chemical parameters were found to be within the limits mentioned in the 98/83/EEC directive. The analysis of biological parameters shows that many of the water samples are inadequate for human consumption because of the presence of bacteria. Cluster analysis (CA) first was used to classify sample sites with similar properties and results in three groups of sites; discriminant analysis (DA) was used to construct the best discriminant functions to confirm the clusters determined by CA and evaluate the spatial variations in water quality. The standard mode discriminant functions, using 17 parameters, yielded classification matrix correctly assigning 96.97% of the cases. In the stepwise mode, the DA produced a classification matrix with 96.36% correct assignments using only ten parameters (EC, Cl^???, NO₃ ^???, HCO₃ ^???, CO₃ ^???2, Ca^?+?2, Na^?+?, Zn, Mn, and Pb). CA and factor analysis (FA) are used to characterize water quality and assist in water quality monitoring planning. CA proved that two major groups of similarity (six subclusters) between 17 physicochemical parameters are formed, and FA extracts six factors that account for 66.478% of the total water quality variation, when all samples’ physicochemical data set is considered. It is noteworthy that the classification scheme obtained by CA is completely confirmed by principal component analysis.     

Assessment of solar driven TiO2-assisted photocatalysis efficiency on amoxicillin degradation

The objective of this work was to evaluate the efficiency of a solar TiO₂-assisted photocatalytic process on amoxicillin (AMX) degradation, an antibiotic widely used in human and veterinary medicine. Firstly, solar photolysis of AMX was compared with solar photocatalysis in a compound parabolic collectors pilot scale photoreactor to assess the amount of accumulated UV energy in the system (Q _UV) necessary to remove 20 mg L^?1 AMX from aqueous solution and mineralize the intermediary by-products. Another experiment was also carried out to accurately follow the antibacterial activity against Escherichia coli DSM 1103 and Staphylococcus aureus DSM 1104 and mineralization of AMX by tracing the contents of dissolved organic carbon (DOC), low molecular weight carboxylate anions, and inorganic anions. Finally, the influence of individual inorganic ions on AMX photocatalytic degradation efficiency and the involvement of some reactive oxygen species were also assessed. Photolysis was shown to be completely ineffective, while only 3.1 kJ_UV?L^?1 was sufficient to fully degrade 20 mg L^?1 AMX and remove 61 % of initial DOC content in the presence of the photocatalyst and sunlight. In the experiment with an initial AMX concentration of 40 mg L^?1, antibacterial activity of the solution was considerably reduced after elimination of AMX to levels below the respective detection limit. After 11.7 kJ_UV?L^?1, DOC decreased by 71 %; 30 % of the AMX nitrogen was converted into ammonium and all sulfur compounds were converted into sulfate. A large percentage of the remaining DOC was in the form of low molecular weight carboxylic acids. Presence of phosphate ions promoted the removal of AMX from solution, while no sizeable effects on the kinetics were found for other inorganic ions. Although the AMX degradation was mainly attributed to hydroxyl radicals, singlet oxygen also plays an important role in AMX self-photosensitization under UV/visible solar light.