Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.     

Significance of platinum group metals emitted from automobile exhaust gas converters for the biosphere

Intention, Goal, Scope, Background  Following the introduction of automobile catalytic converters the platinum group metals (PGM) platinum (Pt), palladium (Pd) and rhodium (Rh) gain on increasing interest in environmental research as these metals are emitted with exhaust fumes into the environment. Consequently, elevated PGM levels were found in different environmental matrices uch as road dusts, soils along heavily frequented roads, sediments of urban rivers etc. Accordingly, the effects of increasing PGM emissions on the biosphere are controversially discussed. Objective  This paper summarizes the present knowledge on the biological availability of PGM to plants and animals. As biological availability is one of the most decisive factors determining the toxicologi-cal potential of xenobiotics, this information is very important to evaluate the possible threat of the noble metals to ecosystems. Results and Discussion  The availability of soluble as well as particle bound PGM to terrestrial plants was demonstrated in several studies. Experimental investigations revealed uptake of Pt, Pd and Rh also by aquatic plants. Additionally, the biological availability of the noble metals for animals has been verified in experimental studies using soluble metal salts, catalytic converter model substances, sediments of urban rivers, road dust or tunnel dust as metal sources. These studies refer mainly to aquatic animals. Beside of free living organisms, in particular worms parasitizing fish demonstrated a high potential to accumulate PGM. This could be of great interest in respect of biomonitoring purposes. Generally, for plants as well as for animals Pd turns out to be the best available metal among the PGM. Compared to other heavy metals, the biological availability of PGM from road dust to zebra mussels(Dreissena polymorpha) ranged between that of Cd and Pb. Conclusion  Especially chronic effects of PGM on the biosphere can not be excluded due to (1) their cumulative increase in the environment, (2) their unexpected high biological availability and bioaccumulation and (3) their unknown toxicological and ecotoxicological potential. However, it appears that acute effects on ecosystems due to anthropogenic PGM emission are not likely. Recommendation and Outlook  Research on environmental PGM contamination of the biosphere, especially the fauna, and on long-term toxiciry of low PGM concentrations is highly appreciated. These studies require very sensitive analytical techniques to determine PGM even in low sample amounts. Research has to be done in particular on reliable determination of (ultra) trace levels of Pd and Rh as the lack of data on these two metals is mainly due to analytical problems.     

Response of bioaerosol cells to photocatalytic inactivation with ZnO and TiO2 impregnated onto Perlite and Poraver carriers

•ZnO/Perlite inactivated 72% of bioaerosols in continuous gas phase. •TiO₂ triggered the highest level of cytotoxicity with 95% dead cells onto Poraver. •Inactivation mechanism occurred by membrane damage, morphological changes and lysis. •ZnO/Poraver showed null inactivation of bioaerosols. •Catalysts losses at the outlet of the photoreactor for all systems were negligible. Bioaerosols are airborne microorganisms that cause infectious sickness, respiratory and chronic health issues. They have become a latent threat, particularly in indoor environment. Photocatalysis is a promising process to inactivate completely bioaerosols from air. However, in systems treating a continuous air flow, catalysts can be partially lost in the gaseous effluent. To avoid such phenomenon, supporting materials can be used to fix catalysts. In the present work, four photocatalytic systems using Perlite or Poraver glass beads impregnated with ZnO or TiO₂ were tested. The inactivation mechanism of bioaerosols and the cytotoxic effect of the catalysts to bioaerosols were studied. The plug flow photocatalytic reactor treated a bioaerosol flow of 460×1 0⁶ cells/m³_air with a residence time of 5.7 s. Flow Cytometry (FC) was used to quantify and characterize bioaerosols in terms of dead, injured and live cells. The most efficient system was ZnO/Perlite with 72% inactivation of bioaerosols, maintaining such inactivation during 7.5 h due to the higher water retention capacity of Perlite (2.8 mL/g_Perlite) in comparison with Poraver (1.5 mL/g_Perlite). However, a global balance showed that TiO₂/Poraver system triggered the highest level of cytotoxicity to bioaerosols retained on the support after 96 h with 95% of dead cells. SEM and FC analyses showed that the mechanism of inactivation with ZnO was based on membrane damage, morphological cell changes and cell lysis; whereas only membrane damage and cell lysis were involved with TiO₂. Overall, results highlighted that photocatalytic technologies can completely inactivate bioaerosols in indoor environments.     

Pesticide and agro-ecological transition: assessing the environmental and human impacts of pesticides and limiting their use

Environmental Science and Pollution Research -     

Pollution historical trends as recorded by sediments at selected sites of the Venice Lagoon

Polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and hexaclorobenzene (HCB) were determined in three sediment cores of the Venice Lagoon: I1, from the San Giuliano Canal that is likely the main source of pollutants for the study area; E, representing the lagoon sediment of the zone of Campalto; and M3, typical of a salt marsh environment and mostly subject to atmospheric inputs. Maximum concentrations were found in core I1: 25-1858 ngI-TE kg(-1) (PCDD/Fs), 1.7-13 microg kg(-1) (HCB), and 107-717 microg kg(-1) (PCBs) are surficial and peak values, respectively. The lagoon sediment (E), is much less contaminated: 24-47 ngI-TE kg(-1) for PCDD/Fs, 2.3-3.6 microg kg(-1) for HCB, and 56-203 microg kg(-1) for PCBs, whereas M3 shows the lowest values: 1.6-6.0 ngI-TE kg(-1) for PCDD/Fs, 0.3-0.6 microg kg(-1) for HCB, and 7.1-39 microg kg(-1) for PCBs. In any case, the recent trend is toward a decrease of pollutant concentration. The chronology of cores E and M3 is based on both 210Pb and 137Cs activity-depth profiles. The maximum concentrations of PCDD/Fs, HCB, and PCBs correspond to the years 1949, 1980, and 1968, respectively. The homologue profiles of PCDD/Fs confirm that I1 has been subject to an industrial source while the other sites also recorded significant contributions, changing over time, of octachlorinated dioxin from combustion. A comparison of the pollutant inventories, all normalised to 210Pb inventories, suggests that the atmospheric contribution to the contamination of the area of Campalto is low: the upper limits range from 6% (PCDD/Fs) to 17% (HCB).     

Genotoxic and cytotoxic in vitro evaluation of ivermectin and its formulation ivomec® on Aedes albopictus larvae (CCL-126™) cells

Genotoxic effects of ivermectin (IVM) and its commercial formulation ivomec® (IVM 1.0%) were studied on Aedes albopictus larvae (CCL-126?) cells by sister chromatid exchange (SCE) and single cell gel electrophoresis (SCGE) while cytotoxicity was determined by cell-cycle progression (CCP), proliferative rate index (PRI), mitotic index (MI), 3(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT), and neutral red (NR) endpoints within a 1–250 µg mL^?1 concentration range. While IVM and ivomec® did not markedly affect SCE frequencies, these agents induced DNA-strand breaks enhancing both slightly damaged and damaged cells at 25–50 and 5–50 µg mL^?1 IVM and ivomec®, respectively. Both compounds exerted a delay in CCP and reduction of PRI at 10 µg mL^?1. Cytotoxicity was observed at concentrations higher than 25 µg mL^?1. A marked reduction of about 98% and 94% of MI compared to controls was noted with 25 µg mL^?1 of IVM and ivomec®, respectively. NR and MTT assays revealed that both compounds induced a cell growth inhibition within the 1–250 µg mL^?1 concentration range. Data indicated that IVM and ivomec® exert both genotoxicity and cytotoxicity in insect cells in vitro, at least in A. albopictus larvae CCL-126? cells.     

Mutagenic activity of transition‐metal complexes: Relation structure‐mutagenic and antibacterial activity for some Pd(II), Pt(II) and Rh(I) complexes†

The inhibitory and mutagenic action of some Pd(II), Pt(II) and Rh(I) complexes towards various bacterial strains has been evaluated, and some correlations have been found between the chemical behaviour of the complexes and their selective biological activity: most of the complexes cause only a DNA damage repaired by the excision repair system. Particularly, the Rh(I) complexes used in this work show selective antibacterial effects on defective but no effect on wild‐type strains.     

Urban land use predicts West Nile virus exposure in songbirds

Urbanization is a widespread phenomenon that is likely to influence the prevalence and impact of wildlife pathogens, with implications for wildlife management and public health policies toward zoonotic pathogens. In this study, wild songbird populations were sampled at 14 sites along an urban rural gradient in the greater metropolitan Atlanta (Georgia, USA) area and tested for antibodies to West Nile virus (WNV). The level of urbanization among sites was quantitatively assessed using a principal component analysis of key land use characteristics. In total, 499 individual birds were tested during the spring and summer over three years (2004-2006). Antibody prevalence of WNV increased from rural to urban sites, and this trend was stronger among adult birds relative to juveniles. Furthermore, antibody prevalence among Northern Cardinals (Cardinalis cardinalis) was significantly higher than in other songbird species along the urban gradient. Findings reported here indicate that ecological factors associated with urbanization can influence infection patterns of this vector-borne viral disease, with likely mechanisms including changes in host species diversity and the tolerance or recovery of infected animals.