Organochlorine concentrations in franciscana dolphins, Pontoporia blainvillei, from Brazilian waters

Blubber samples were collected from ten franciscana dolphins either incidentally captured in fishing operations or stranded on São Paulo (SP) and Paraná (PR) states littoral, Southeastern and Southern Brazilian coast, respectively. Determination of PCB, DDT and HCB concentrations were performed by capillary gas chromatograph coupled to electron capture detector (ECD). ΣDDT, ΣPCB and HCB concentrations ranged from 264 ng g⁻¹ to 5811 ng g⁻¹ lipid, from 909 ng g⁻¹ to 5849 ng g⁻¹ lipid and from 10 ng g⁻¹ to 61 ng g⁻¹ lipid, respectively. Regarding DDTs, the distribution of the mean percentages decreased in the following order: p,p′-DDE > p,p′-DDD > p,p′-DDT. The ΣDDT/ΣPCB ratio varied between 0.27 and 0.42 in Northern and Central SP coast, while in Southern SP and PR coast the values were 1.6 and 1.9, respectively. Dissimilarities in ΣDDT/ΣPCB ratios point to different sources of organochlorine compounds to franciscana dolphins in the study area. Considering the endocrine disruptive action of organochlorine compounds, the concentrations found in franciscana dolphins from Brazilian waters may represent an additional obstacle to the conservation of this endangered cetacean species.     

Degradation of carbofuran and carbofuran-derivatives in presence of humic substances under basic conditions

The influence of humic aggregates in water solution upon the chemical stability of carbofuran (CF) and the carbofuran-derivatives, 3-hydroxy-carbofuran (HCF) and 3-keto-carbofuran (KCF), has been investigated in basic media. An inhibition upon the basic hydrolysis of 3-hydroxy-carbofuran and 3-keto-carbofuran (∼1.7 and ∼1.5-fold, respectively) was observed and it was rationalized in terms of the micellar pseudophase model. Nevertheless, non-significant effect upon the carbofuran stability was found in the presence of humic substances. These behaviors have been compared with the corresponding ones in other synthetic colloidal aggregates.     

Characterization of the olfactory impact around a wastewater treatment plant: Optimization and validation of a hydrogen sulfide determination procedure based on passive diffusion sampling

A monitoring program based on an indirect method was conducted to assess the approximation of the olfactory impact in several wastewater treatment plants (in the present work, only one is shown). The method uses H₂S passive sampling using Palmes-type diffusion tubes impregnated with silver nitrate and fluorometric analysis employing fluorescein mercuric acetate. The analytical procedure was validated in the exposure chamber. Exposure periods of at least 4 days are recommended. The quantification limit of the procedure is 0.61 ppb for a 5-day sampling, which allows the H₂S immission (ground concentration) level to be measured within its low odor threshold, from 0.5 to 300 ppb. Experimental results suggest an exposure time greater than 4 days, while recovery efficiency of the procedure, 93.0 ± 1.8%, seems not to depend on the amount of H₂S collected by the samplers within their application range. The repeatability, expressed as relative standard deviation, is lower than 7%, which is within the limits normally accepted for this type of sampler. Statistical comparison showed that this procedure and the reference method provide analogous accuracy. The proposed procedure was applied in two experimental campaigns, one intensive and the other extensive, and concentrations within the H₂S low odor threshold were quantified at each sampling point. From these results, it can be concluded that the procedure shows good potential for monitoring the olfactory impact around facilities where H₂S emissions are dominant.

Implications: Passive samplers are very attractive tools to experimentally tackle a number of air pollution problems, especially those related to odor impact. Their small size and cost permit a denser sampling design and thus a more detailed spatial characterization than other techniques. On the other hand, the large inherent variability in passive sampler measures requires an uncertainty analysis of the chemical species and analytical procedures used.     

Cyclooctane tropospheric degradation initiated by reaction with Cl atoms

Goal, Scope and Background Within the non-methane hydrocarbons, alkanes constitute the largest fraction of the anthropogenic emissions of volatile organic compounds. For the case of cyclic alkanes, tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atom reaction rate constants are generally one order of magnitude larger than those of OH. In the present work, the reaction of cyclooctane with Cl atoms has been studied within the temperature range of 279–333 K. Methods The kinetic study has been carried out using the fast flow tube technique coupled to mass spectrometry detection. The reaction has been studied under low pressure conditions, p=1 Torr, with helium as the carrier gas. Results The measured room temperature rate constant is very high, k=(2.63±0.54)×10⁻¹⁰ cm³molecule⁻¹s⁻¹, around 20 times larger than that for the corresponding OH reaction. We also report the results of the rate coefficients obtained at different temperatures: k = (3.5±1.2)×10⁻¹⁰ exp[(−79±110)/T] cm³ molecule⁻¹ s⁻¹ within the range of 279–333 K. This reaction shows an activation energy value close to zero. Discussion Quantitative formation of HCl has been observed, confirming the mechanism through H-atom abstraction. The reactivity of cyclic alkanes towards Cl atoms is clearly dependent on the number of CH₂ groups in the molecule, as is shown by the increase in the rate constant when the length of the organic chain increases. This increase is very high for the small cyclic alkanes and it seems that the reactions are approaching the collision-controlled limit for cyclohexane and cyclooctane. Conclusions These results show that gas-phase reaction with Cl in marine or coastal areas is an efficient sink (competing with the gas phase, OH initiated degradation) for the Earth’s emissions of cyclooctane, with a Cl-based lifetime ranging from 11 to 2000 hours, depending on the location and time of day. Recommendations and Perspectives Cl and OH fast reactions with cyclooctane are expected to define the lifetime of cyclooctane emissions to the atmosphere. The degradation of cyclooctane occurs in a short period of time and consequently (under conditions of low atmospheric mass transport), close to the emission sources enabling a significant contribution to local effects, like the formation of photochemical smog. ESS-Submission Editor: Prof. Dr. Gerhard Lammel (lammel@recetox.muni.cz)     

The impact of synthetic pyrethroid and organophosphate sheep dip formulations on microbial activity in soil

Sheep dip formulations containing organophosphates (OPs) or synthetic pyrethroids (SPs) have been widely used in UK, and their spreading onto land has been identified as the most practical disposal method. In this study, the impact of two sheep dip formulations on the microbial activity of a soil was investigated over a 35-d incubation. Microbial utilisation of [1-(14)C] glucose, uptake of (14)C-activity into the microbial biomass and microbial numbers (CFUs g(-1) soil) were investigated. In control soils and soils amended with 0.01% sheep dip, after 7d a larger proportion of added glucose was allocated to microbial biomass rather than respired to CO(2). No clear temporal trends were found in soils amended with 0.1% and 1% sheep dips. Both sheep dip formulations at 0.1% and 1% concentrations resulted in a significant increase in CFUs g(-1) soil and [1-(14)C] glucose mineralisation rates, as well as a decline in microbial uptake of [1-(14)C] glucose, compared to control and 0.01% SP- or OP-amended soils. This study suggests that the growth, activity, physiological status and/or structure of soil microbial community may be affected by sheep dips.     

Simulation of the influence of industrial wastewater on a municipal sewage treatment plant—a case study

Purpose  

Industrial wastewater flow caused operational difficulties in the wastewater treatment plant in Debrecen, Hungary. Bioaugmentation was successfully applied to maintain effluent quality in the periods when wastewater of high starch content was accepted, but, at the end of 2008, the nitrification capacity of the plant decreased considerably due to improperly pre-treated pharmaceutical wastewater.     

Well-designed environmental regulation and firm performance: Swedish evidence on the Porter hypothesis and the effect of regulatory time strategies

Using recent data on a cross-section of Swedish chemical and pulp and paper firms, this paper provides novel empirical insights into the Porter hypothesis. Well-designed environmental regulation can stimulate firms’ innovative capabilities, while at the same time generating innovation offsets that may both offset net compliance costs and yield a competitive edge over those firms that are not affected by such regulations. In doing so, we also test the alleged effectiveness of regulatory time strategies in stimulating innovation activities of regulated firms. We find evidence for the effectiveness of such well-designed regulations: announced rather than existing regulation induces innovation and some innovation offsets. Our results imply that empirical tests of the Porter hypothesis that do not account for its dynamic nature, and that do not measure well-designed regulations, might provide misleading conclusions as to its validity.     

Adsorption of Mn2+ from aqueous solution using Fe and Mn oxide-coated sand

The adsorption of Mn²⁺ onto immobilized Mn-oxide and Fe-oxide adsorbent such as manganese oxide-coated sand1 (MOCS1), manganese oxide-coated sand2 (MOCS2), iron oxide-coated sand2 (IOCS2), and manganese and iron oxide-coated sand (MIOCS) was investigated. The effects of pH (5.5 to 8.0) and temperature (25 to 45℃) on the equilibrium capacity were examined. Equilibrium studies showed that there is a good fit with both Freundlich and Langmuir isotherm, which indicates surface heterogeneity and monolayer adsorption of the adsorbents. Kinetic data showed high correlation with the pseudo second-order model, which signifies a chemisorption-controlled mechanism. The activation energies, activation parameters (ΔG^*, ΔH^*, ΔS^*), and thermodynamic parameters (ΔG⁰, ΔH⁰, ΔS⁰) confirmed that adsorption with MIOCS was endothermic and more spontaneous at higher temperature while an opposite trend was observed for the other adsorbents. Thermodynamic studies showed that adsorption involved formation of activated complex, where MOCS1 and MIOCS follow a physical-chemical mechanism, while MOCS2 and IOCS2 follows purely chemical mechanism.