Mobilization of arsenic in groundwater of Bangladesh: evidence from an incubation study

The extensive extraction of arsenic (As)-contaminated groundwaters for drinking, household and agricultural purposes represents a serious health concern in many districts of Bangladesh. This laboratory-based incubation study investigated the sources and mechanisms of As mobilization in these groundwaters. Several incubation studies were carried out using sediments collected from the Bangladesh aquifer that were supplemented, or not, with different nutrients, followed by an analysis of the sediment suspensions for pH, ORP (oxidation-reduction potential), EC (electrical conductivity) and As and Fe(ΙΙ) concentrations. In the substrate-amended sediment suspensions incubated under anaerobic environment, there was a mobilization of As (maximum: 50–67 μg/l) and Fe(ΙΙ) (maximum: 182 μg/l), while the ORP value decreased immediately and drastically (as much as −468 mV to −560 mV) within 5–6 days. In the sediment suspensions incubated under control and aerobic conditions, no significant As mobilization occurred. The simultaneous mobilization of As and Fe(ΙΙ) from sediments is a strong indication that their mobilization resulted from the reduction of Fe oxyhydroxide by the enhanced activity of indigenous bacteria present in the sediments; this phenomenon also provides insights on the mobilization mechanism of As in groundwater. The concentrations of As in the sediments used in the incubation studies were strongly linked to the gradients of redox potential development that was stimulated by the quantity of organic nutrient (glucose) used. The penetration of surface-derived organic matter into the shallow aquifer may stimulate the activity of microbial communities, thereby leading to a reduction of iron oxyhydroxide and As release.     

Seasonal pattern of metal bioaccumulation and their toxicity on Sphagnum squarrosum

Present study was undertaken as an attempt to study the effect of pollutants on biological responses of Sphagnum growing at Kainchi, Kumaon hills (Uttranchal). Sphagnum plants of almost identical size, collected from the marked sites of Kainchi in different seasons viz., monsoon, winter, summer and again in monsoon, were analysed for chlorophyll, protein, shoot length and nitrate reductase and peroxidase activities. Maximum chlorophyll, protein, shoots length and nitrate reductase activities were observed during the monsoon while minimum in summers. The abundance of Sphagnum and two other bryophytes, Marchantia and Plagiochasma was also higher in monsoon than in other seasons. The study also indicated that Sphagnum has more bioaccumulation and tolerance potential for heavy metals than Marchantia and Plagiochasma.     

Formation of dioxins from combustion of polyvinylidene chloride in a well-controlled incinerator

Polyvinylidene chloride (PVDC; polymer of 1,1-dichloroethylene) was combusted with paper in a well-controlled, small-scale incinerator at an average grate temperature of 700 °C, and then dioxins (PCDDs, PCDFs, and coplanar-PCBs) formed in the exhaust gases were analyzed by gas chromatography/mass spectrometry. PVDC lowered the combustion temperature due to its less flammable character. The amount of total dioxins (PCDDs + PCDFs + coplanar-PCBs) formed in the exhaust gas was 58.0 ng/g of a combustion sample and its toxicity equivalency quantity (TEQ) value was 0.64 ng-TEQ/g. The amount of PCDDs formed in the sample ranged from 2.33 ng/g (Cl₈-isomer) to 0.048 ng/g (Cl₁-isomer). The lower the number of chloride, the less production of PCDDs. On the other hand, there was no relation between the number of chloride and PCDF formation. The amount of PCDFs formed in the sample ranged from 8.02 ng/g (Cl₂-isomer) to 4.46 ng/g (Cl₈-isomer). A polyvinylchloride (PVC) sample produced 207 ng/g of total dioxins and a PVDC sample produced 57.4 ng/g of total dioxins when they were combusted under the same conditions. An approximately equal composition of dioxin isomers was formed from PVDC and PVC samples. Paper was found to contribute to PCDF formation when it was combusted with plastics.     

Elemental characterization of PM10, PM2.5 and PM1 in the town of Genoa (Italy)

The particulate matter (PM) concentration and composition, the PM10, PM2.5, PM1 fractions, were studied in the urban area of Genoa, a coastal town in the northwest of Italy. Two instruments, the continuous monitor TEOM and the sequential sampler PARTISOL, were operated almost continuously on the same site from July 2001 to September 2004. Samples collected by PARTISOL were weighted to obtain PM concentration and then analysed by PIXE (particle induced X-ray emission) and by ED-XRF (energy dispersion X-ray fluorescence), obtaining concentrations for elements from Na to Pb. Some of the filters used in the TEOM microbalance were analysed by ED-XRF to calculate Pb concentration values averaged over 7-30 d periods.     

Isoprene emission from tropical trees in Okinawa Island, Japan

This study surveyed isoprene emission from 42 indigenous and exotic tropical trees in subtropic Okinawa, Japan. Of the 42 trees studied, 4 emitted isoprene at a rate in excess of 20 μg g⁻¹ h⁻¹, and 28 showed the rates of 1–10 μg g⁻¹ h⁻¹. The remainder emitted less than 1 μg g⁻¹ h⁻¹. The majority of trees in this study may therefore fall within the lower emitting species. However, species in Moraceae that is indigenous in Okinawa emitted isoprene at relatively higher rates with an average of 14.2 μg g⁻¹ h⁻¹. The highest emission rate of 107.1 μg g⁻¹ h⁻¹ for Ficus virgata yielded the area basis rate of 47.4 nmol m⁻² s⁻¹, which is almost equivalent to the rate of high emitting species. Furthermore, a linear relationship between light intensity and isoprene emission was noted with Ficus virgata up to 1700 μmol m⁻² s⁻¹. These findings may show the potential importance of subtropical areas as sources of isoprene to the atmosphere.     

Identification of hydroxylated metabolites in 2,2',4,4'-tetrabromodiphenyl ether exposed rats

Faeces from day 1-5 of orally administered 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) in rat have been analysed for hydroxylated metabolites. Six hydroxylated tetrabrominated diphenyl ethers, as well as three hydroxylated tribrominated diphenyl ethers found, were structurally identified. They were 2'-hydroxy-2,4,4'-tribromodiphenyl ether, 3'-hydroxy-2,4,4'-tribromodiphenyl ether, 4'-hydroxy-2,2',4-tribromodiphenyl ether, 6-hydroxy-2,2',4,4'-tetrabromodiphenyl ether, 2'-hydroxy-2,3',4,4'-tetrabromodiphenyl ether, 3-hydroxy-2,2',4,4'-tetrabromodiphenyl ether, 5-hydroxy-2,2',4,4'-tetrabromodiphenyl ether, 4'-hydroxy-2,2',4,5'-tetrabromodiphenyl ether and 4-hydroxy-2,2',3,4'-tetrabromodiphenyl ether. The analysis was performed using gas chromatography-mass spectrometry (GC-MS). The identification of the hydroxylated polybrominated diphenyl ether (OH-PBDE) metabolites in the rat faeces was supported by similar relative retention times (RRTs) versus 2,2',3,4,4',5-hexabromodiphenyl ether (BDE-138) on two columns of different polarities compared to the authentic references. The identification of the OH-PBDE metabolites was also supported by full scan electron ionisation mass spectra. Two of the identified OH-PBDE metabolites have identical structures as natural products, which previously have been isolated from marine sponges and an ascidian.     

Transfer of nutrients and labile metals from the continent to the sea by a small Mediterranean river

The contribution of small watersheds to coastal pollution in Mediterranean areas is still poorly known, and presents great variations along an hydrological year. This work deals with the characterization and quantification of Al, Fe, Zn, Cu, Pb, Si, NO(3)(-) and organic carbon transported from the continent to the sea by a small coastal river in the French Mediterranean area. Transported species were characterized both during rainy and dry periods. During non-rainy periods (base-flow), waters showed a low content of contaminants, whereas during heavy rain events, following dry periods, some metals and organic carbon reached concentrations that could affect biological populations. These contaminants were mainly found in the particulate fraction, originating from the runoff of surface waters, which represents the main process of pollution in urban areas.     

Degradation of CL-20 by white-rot fungi

In previous studies, we found that the emerging energetic chemical, CL-20 (C6H6N12O12, 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane), can be degraded following its initial denitration using both aerobic and anaerobic bacteria. The C and N mass balances were not determined due to the absence of labeled starting compounds. The present study describes the degradation of the emerging contaminant by Phanerochaete chrysosporium using ring-labeled [15N]-CL-20 and [14C]-CL-20. Ligninolytic cultures degraded CL-20 with the release of nitrous oxide (N2O) in amounts corresponding to 45% of the nitrogen content of CL-20. When ring-labeled [15N]-CL-20 was used, both 14N14NO and 15N14NO were observed, likely produced from -NO2 and N-NO2, respectively. The incubation of uniformly labeled [14C]-CL-20 with fungi led to the production of 14CO2 (> 80%). Another ligninolytic fungus, Irpex lacteus, was also able to degrade CL-20, but as for P. chrysosporium, no early intermediates were observed. When CL-20 was incubated with manganese peroxidase (MnP), we detected an intermediate with a [M-H]- mass ion at 345 Da (or 351 and 349 Da when using ring-labeled and nitro-labeled [15N]-CL-20, respectively) matching a molecular formula of C6H6N10O8. The intermediate was thus tentatively identified as a doubly denitrated CL-20 product. The concomitant release of nitrite ions (NO2-) with CL-20 degradation by MnP also supported the occurrence of an initial denitration prior to cleavage and decomposition.     

Influence of the very polluted inputs of the Tinto-Odiel system on the adjacent littoral sediments of southwestern Spain: a statistical approach

A spatial and temporal analysis (period 1990-2003) of 15 sampling points distributed along the southwestern Spanish coast permits to delimitate the influence area of the extremely polluted discharges coming from the Tinto-Odiel system in the bottom sediments of the adjacent littoral area. As, Cu, Pb and Zn are the main heavy metals transported by the freshwater runoffs toward the shallow shelf and present very high negative (r < -0.7) and significant (p < 0.001) correlations with the distance to the estuarine mouth. The statistical analysis (index of geoaccumulation, Pearson correlation matrix, cluster analysis) of their concentrations in the littoral sediments located between the Guadiana and Guadalquivir mouths delimitates three zones: (a) Zone 1 (from the estuarine mouth to 6 km to the east), characterized by moderate to strongly polluted bottom sediments and main responsible of the mean annual variations of the former heavy metals in the area studied; (b) Zone 2 (from 21.2 km to the west to 29 km to the east), characterized by moderate pollution levels; and (c) Zone 3, located near the Guadiana and Guadalquivir mouths, with very low As-Cu-Pb contents and unpolluted to moderately levels of Zn due to urban sewages or the presence of local low mobility areas for this element.     

Copper binding by peat fulvic and humic acids extracted from two horizons of an ombrotrophic peat bog

We studied the binding of Cu(II) to humic acids and fulvic acids extracted from two horizons of an ombrotrophic peat bog by metal titration experiments at pH 4.5, 5.0, 5.5, and 6.0 and 0.1 M KNO3 ionic strength. Free metal ion concentrations in solution were measured using an ion selective electrode. The amounts of base required to maintain constant pH conditions were recorded and used to calculate H+/Cu2+ exchange ratios. The amount of Cu(II) bound to the humic fractions was greater than the amount bound to the fulvic fractions and only at the highest concentrations of metal ion the amount of Cu(II) sorbed by both fractions became equal. The proton to metal ion exchange ratios are similar for all humic substances, with values ranging from 1.0 to 2.0, and decreasing with increased pH. The amount of Cu(II) bound is practically independent of the horizon from which the sample was extracted. The results indicate that the humic substances show similar cation binding behaviour, despite the differences in chemical composition. The copper binding data are quantitatively described with the NICA-Donnan model, which allows to characterize only the carboxylic type binding sites. The values of the binding constants are higher for the humic acids than for the fulvic acids.