Multivariate characterization of polycyclic aromatic hydrocarbons using semi-empirical molecule orbital calculations and physical data

Multivariate characterization of 60 polycyclic aromatic hydrocarbons (PAHs) was performed using data from literature and semi-empirical molecular orbital calculations. This dataset was analyzed by principal component analysis and projections to latent structures by means of partial least square. The PAHs were found to distribute in the chemical domain in several groups mainly governed by the number of aromatic rings and the number of five-membered rings. The multivariate model and training set was used to predict GC retention times on a non-polar column (DB-5). Using a 2(4) experimental design on the principal components of the chemical characterization model, a test set of PAHs was selected dependent on the distribution in the chemical domain of the PAHs. Such a test set is expected to improve selection of PAHs for future testing and modeling of both biological and chemical responses. Although the model of GC retention times was good, the precision was however not good enough for practical use.     

A new structure-affinity relationship for TCDD receptor binding

We have investigated the capacity of various indoles to inhibit specific binding of [1,6-³H]2,3,7,8-tetrachlorodibenzo- -dioxin ([³H]TCDD) in rat liver cytosol, as analyzed by electrofocusing in polyacrylamide gels. Of these indoles, indolo[3,2- ]carbazole was the most active. The IC₅₀ value for TCDD receptor binding of indolo[3,2- ]carbazole as well as for 2,3,7,8-tetrachlorodibenzofuran was 3.6 nM. We have also studied the influence on binding exerted by introduction of some substituents on indolo[3,2- ]carbazole. Substitution with methyl groups at the 5 and 11 positions resulted in an increased affinity (IC₅₀ 1.2 nM) for the TCDD receptor as compared to the parent compound. Computer-supported molecular structure studies indicated that if the van der Waals radii of atoms are included, a rectangle of 6.8 × 13.7 Å may account for the binding of high-affinity ligands to the TCDD receptor.     

Common Patterns of Ecosystem Breakdown Under Stress

Ecosystems, despite their diversity, respond to stress in similar ways. The major pressures which cause the transformation of systems from healthy states to pathological states are classified into four groups: physical restructuring, overharvesting, waste residuals, and the introduction of non-native species. Signs of Ecosystem Distress Syndrome (EDS) are briefly examined in three contrasting ecosystems: desert grasslands, the Great Lakes, and the Baltic Sea. The issue is raised as to the difficulty in discerning between healthy ecosystems, recovering from a natural disturbance, and those ecosystems that have lost their original resilience due to anthropogenic stress. Knowledge of site history and a rigourous monitoring program are important in the evaluation of EDS. An assessment of how ecosystem services are affected is indicative of the consequences to the human component of ecosystems. Management strategies which are employed to mitigate the signs of EDS are usually initiated after resilience is lost or the ecosystem has transformed to an alternate, stress-induced, stable state. It is proposed that preventive strategies measure signs of EDS that serve as early warning signals, combined with "fitness tests" that measure ecosystem response to natural perturbations. The fitness test for ecosystems is based on the premise that unstressed systems are more resilient to natural disturbances than stressed systems.     

Diversifying forest expertise: forest journals narrating policy change

ABSTRACT

During policy change, the role of the actors communicating the change to different audiences is accentuated. The media plays an increasing role, either as an actor or by providing a stage for other actors. In particular, specialised journals represent an influential, albeit understudied, sphere of policy studies. We use the narrative policy framework complemented with frame analysis to trace how specialised media can affect policy implementation through implicit suggestions for action. Using this combined approach, we analyse how specialised forest journals, which are the most important forest information source for Finnish forest owners, have conveyed the renewal of forest legislation in Finland. The core message of the journals is that forest owners should, despite their new freedom granted by the reform, rely on experts rather than experimenting when managing their forests. This suggests that the media contributes to a path-dependent continuation of a forest policy that is based on a rationalistic exploitation ethos. The innovative potential, which the policy change aimed at encouraging, is thereby partially undermined. However, the analysis of the narratives also reveals that forest expertise and professionalism are diversifying. This notion is important as diversity can eventually lead to narratives supporting more fundamental change in forests management.     

Acidification and recreational fisheries in Finland: A mail survey of potential impacts

In Finland, small forest lakes and rivers in the northern part of the country are more sensitive to acidic deposition than other Finnish waters. In some lakes, acid-sensitive fish populations have declined. A nationwide survey of fishers showed that, at present, the number of fishers whose primary fishing waters are affected by airborne acidification is negligible compared to the estimated total number of adult fishers (1.1 million). The proportion of the fishers who mainly fish in water types sensitive to airborne acidification is considerable, 3% for the rivers in northern Finland and 21% for small forest lakes. There is general concern among fishers about the effects of acidification. Changes in the fishing waters are attributed to acidification by 5–10% of the fishers, although in most cases other information about the fishing waters rules out acidification as an explanation for the changes. Among those who fish in sensitive types of waters, a willingness to mitigate potential damages was reported by approximately one third of all fishers. Clear differences in the willingness to rehabilitate the fishery were observed in relation to the importance of fishing as a spare time activity and the distance between the fishing waters and a home or summer cottage.     

The use of sewage sludge as remediation for imidacloprid toxicity in soils

Environmental Science and Pollution Research - This study investigated the influence of the sewage sludge (SS) soil amendment on the chronic toxicity of imidacloprid (through the seed dressing...     

Potentially toxic element fractionation in technosoils using two sequential extraction schemes

This study reports the chemical fractionation of several potentially toxic elements (Zn, Pb, Cd, As, and Sb) in contaminated technosoils of two former smelting and mining areas using two sequential extraction schemes. The extraction schemes used in this study were the Tessier’s scheme and a modified BCR scheme. The fractions were rearranged into four equivalent fractions defined as acid soluble, reducible, oxidizable, and residual to compare the results obtained from two sequential extraction schemes. Surface soils were samples from a waste landfill contaminated with Zn, Pb, and Cd located at Mortagne-du-Nord (MDN; North France) and from a settling basin contaminated with PTE such as As, Pb, and Sb located at La Petite Faye (LPF; Limoges, France). The study of the Zn, Pb, Cd, As, and Sb partitioning in the acid soluble, reducible, oxidizable, and residual fractions of the technosoils revealed that Zn, Cd, and Pb were mainly associated with the acid soluble and reducible fractions for MDN site, while As, Sb, and Pb were associated with residual fraction for LPF site. Fractionation results indicate that the percentages of Zn, Pb, Cd, As, and Sb extracted in Fe–Mn oxide bound fraction of Tessier’s scheme were always higher than those extracted by modified BCR scheme. This may be attributed to the stronger Tessier’s scheme conditions used to extract this fraction. In contrast the percentages of Zn, Pb, Cd, As, and Sb extracted in the organic fraction of the modified BCR scheme were always higher than those of the Tessier’s scheme. The order of mobility of PTE was as follows: Cd?>?Zn?>?Pb in MDN site and As?>?Sb?>?Pb in LPF site. PTE were distributed in all soil fractions, with the most relevant enrichments in extractable and residual fractions. A significant amount of Cd, Pb, and Zn were rather mobile, which suggests that these elements can be readily available to plants and soil organisms.     

Mobility and phytoavailability of Cu,Cr, Zn,and As in a contaminated soil at a wood preservation site after 4 years of aided phytostabilization

The remediation of copper-contaminated soils by aided phytostabilisation in 16 field plots at a wood preservation site was investigated. The mobility and bioavailability of four potentially toxic trace elements (PTTE), i.e., Cu, Zn, Cr, and As, were investigated in these soils 4 years after the incorporation of compost (OM, 5 % w/w) and dolomite limestone (DL, 0.2 % w/w), singly and in combination (OMDL), and the transplantation of mycorrhizal poplar and willows. Topsoil samples were collected in all field plots and potted in the laboratory. Total PTTE concentrations were determined in soil pore water (SPW) collected by Rhizon soil moisture samplers. Soil exposure intensity was assessed by Chelex100-DGT (diffusive gradient in thin films) probes. The PTTE phytoavailability was characterized by growing dwarf beans on potted soils and analyzing their foliar PTTE concentrations. OM and DL, singly and in combination (OMDL), were effective to decrease foliar Cu, Cr, Zn, and As concentrations of beans, the lowest values being numerically for the OM plants. The soil treatments did not reduce the Cu and Zn mineral masses of the bean primary leaves, but those of Cr and As decreased for the OM and DL plants. The Cu concentration in SPW was increased in the OM soil and remained unchanged in the DL and OMDL soils. The available Cu measured by DGT used to assess the soil exposure intensity correlated with the foliar Cu concentration. The Zn concentrations in SPW were reduced in the DL soil. All amendments increased As in the SPW. Based on DGT data, Cu availability was reduced in both OM and OMDL soils, while DL was the most effective to decrease soil Zn availability.     

Current and emerging strategies for organophosphate decontamination: special focus on hyperstable enzymes

Organophosphorus chemicals are highly toxic molecules mainly used as pesticides. Some of them are banned warfare nerve agents. These compounds are covalent inhibitors of acetylcholinesterase, a key enzyme in central and peripheral nervous systems. Numerous approaches, including chemical, physical, and biological decontamination, have been considered for developing decontamination methods against organophosphates (OPs). This work is an overview of both validated and emerging strategies for the protection against OP pollution with special attention to the use of decontaminating enzymes. Considerable efforts have been dedicated during the past decades to the development of efficient OP degrading biocatalysts. Among these, the promising biocatalyst SsoPox isolated from the archaeon Sulfolobus solfataricus is emphasized in the light of recently published results. This hyperthermostable enzyme appears to be particularly attractive for external decontamination purposes with regard to both its catalytic and stability properties.