Multivariate toxicity profiles and QSAR modeling of non-dioxin-like PCBs--an investigation of in vitro screening data from ultra-pure congeners

The non-dioxin-like PCBs (NDL-PCBs) found in food and human samples have a complex spectrum of adverse effects, but lack a detailed risk assessment. The toxicity profiles of 21 carefully selected PCBs (19 NDL-PCBs) were identified by in vitro screening in 17 different assays on specific endpoints related to neurotoxicity, endocrine disruption and tumor promotion. To ensure that the test results were not affected by polychlorinated dioxins, dibenzofurans or DL-PCB contaminants, the NDL-PCB congeners were thoroughly purified before testing. Principal component analysis (PCA) was used to derive general toxicity profiles from the in vitro screening data. The toxicity profiles indicated different structure-activity relationships (SAR) and distinct mechanisms of action. The analysis also indicated that the NDL-PCBs could be divided into two groups. The first group included generally smaller, ortho-substituted congeners, comprising PCB 28, 47, 51, 52, 53, 95, 100, 101, 104 and 136, with PCB 95, 101 and 136 as generally being most active. The second group comprising PCB 19, 74, 118, 122, 128, 138, 153, 170, 180 and 190 had lower biological activity in many of the assays, except for three endocrine-related assays. The most abundant congeners, PCB 138, 153, 170, 180 and 190, cluster in the second group, and thereby show similar SAR. Two quantitative structure-activity relationship (QSAR) models could be developed that added information to the SAR and could aid in risk assessments of NDL-PCBs. The QSAR models predicted a number of congeners as active and among these e.g., PCB 18, 25, 45 and 49 have been found in food or human samples.     

Urban tinkering

Cities are currently experiencing serious, multifaceted impacts from global environmental change, especially climate change, and the degree to which they will need to cope with and adapt to such challenges will continue to increase. A complex systems approach inspired by evolutionary theory can inform strategies for policies and interventions to deal with growing urban vulnerabilities. Such an approach would guide the design of new (and redesign of existing) urban structures, while promoting innovative integration of grey, green and blue infrastructure in service of environmental and health objectives. Moreover, it would contribute to more flexible, effective policies for urban management and the use of urban space. Four decades ago, in a seminal paper in Science, the French evolutionary biologist and philosopher Francois Jacob noted that evolution differs significantly in its characteristic modes of action from processes that are designed and engineered de novo (Jacob in Science 196(4295):1161–1166, 1977). He labeled the evolutionary process “tinkering”, recognizing its foundation in the modification and molding of existing traits and forms, with occasional dramatic shifts in function in the context of changing conditions. This contrasts greatly with conventional engineering and design approaches that apply tailor-made materials and tools to achieve well-defined functions that are specified a priori. We here propose that urban tinkering is the application of evolutionary thinking to urban design, engineering, ecological restoration, management and governance. We define urban tinkering as:

A mode of operation, encompassing policy, planning and management processes, that seeks to transform the use of existing and design of new urban systems in ways that diversify their functions, anticipate new uses and enhance adaptability, to better meet the social, economic and ecological needs of cities under conditions of deep uncertainty about the future.

This approach has the potential to substantially complement and augment conventional urban development, replacing predictability, linearity and monofunctional design with anticipation of uncertainty and non-linearity and design for multiple, potentially shifting functions. Urban tinkering can function by promoting a diversity of small-scale urban experiments that, in aggregate, lead to large-scale often playful innovative solutions to the problems of sustainable development. Moreover, the tinkering approach is naturally suited to exploring multi-functional uses and approaches (e.g., bricolage) for new and existing urban structures and policies through collaborative engagement and analysis. It is thus well worth exploring as a means of delivering co-benefits for environment and human health and wellbeing. Indeed, urban tinkering has close ties to systems approaches, which often are recognized as critical to sustainable development. We believe this concept can help forge much-closer, much-needed ties among engineers, architects, evolutionary ecologists, health specialists, and numerous other urban stakeholders in developing innovative, widely beneficial solutions for society and contribute to successful implementation of SDG11 and the New Urban Agenda.

     

Pure non-dioxin-like PCB congeners suppress induction of AhR-dependent endpoints in rat liver cells

The relative potencies of non-ortho-substituted coplanar polychlorinated biphenyl (PCB) congeners to activate the aryl hydrocarbon receptor (AhR) and to cause the AhR-dependent toxic events are essential for their risk assessment. Since some studies suggested that abundant non-dioxin-like PCB congeners (NDL-PCBs) may alter the AhR activation by PCB mixtures and possibly cause non-additive effects, we evaluated potential suppressive effects of NDL-PCBs on AhR activation, using a series of 24 highly purified NDL-PCBs. We investigated their impact on the model AhR agonist-induced luciferase reporter gene expression in rat hepatoma cells and on induction of CYP1A1/1B1 mRNAs and deregulation of AhR-dependent cell proliferation in rat liver epithelial cells. PCBs 128, 138, and 170 significantly suppressed AhR activation (with IC₅₀ values from 1.4 to 5.6 μM), followed by PCBs 28, 47, 52, and 180; additionally, PCBs 122, 153, and 168 showed low but still significant potency to reduce luciferase activity. Detection of CYP1A1 mRNA levels in liver epithelial cells largely confirmed these results for the most abundant NDL-PCBs, whereas the other AhR-dependent events (CYP1B1 mRNA expression, induction of cell proliferation in confluent cells) were less sensitive to NDL-PCBs, thus indicating a more complex regulation of these endpoints. The present data suggest that some NDL-PCBs could modulate overall dioxin-like effects in complex mixtures.     

Alternating Copolymers and Alternative Device Geometries for Organic Photovoltaics

Bathymetry, the underwater topography, is a fundamental property of oceans, seas, and lakes. As such it is important for a wide range of applications, like physical oceanography, marine geology, geophysics and biology or the administration of marine resources. The exact requirements users may have regarding bathymetric data are, however, unclear. Here, the results of a questionnaire survey and a literature review are presented, concerning the use of Baltic Sea bathymetric data in research and for societal needs. It is demonstrated that there is a great need for detailed bathymetric data. Despite the abundance of high-quality bathymetric data that are produced for safety of navigation purposes, the digital bathymetric models publicly available to date cannot satisfy this need. Our study shows that DBMs based on data collected for safety of navigation could substantially improve the base data for administrative decision making as well as the possibilities for marine research in the Baltic Sea.     

AhR agonist and genotoxicant bioavailability in a PAH-contaminated soil undergoing biological treatment

Background, aim, and scope  Degradation of the 16 US EPA priority PAHs in soil subjected to bioremediation is often achieved. However, the PAH loss is not always followed by a reduction in soil toxicity. For instance, bioanalytical testing of such soil using the chemical-activated luciferase gene expression (CALUX) assay, measuring the combined effect of all Ah receptor (AhR) activating compounds, occasionally indicates that the loss of PAHs does not correlate with the loss of Ah receptor-active compounds in the soil. In addition, standard PAH analysis does not address the issue of total toxicant bioavailability in bioremediated soil. Materials and methods  To address these questions, we have used the CALUX AhR agonist bioassay and the Comet genotoxicity bioassay with RTL-W1 cells to evaluate the toxic potential of different extracts from a PAH-contaminated soil undergoing large-scale bioremediation. The extracts were also chemically analyzed for PAH16 and PCDD/PCDF. Soil sampled on five occasions between day 0 and day 274 of biological treatment was shaken with n-butanol with vortex mixing at room temperature to determine the bioavailable fraction of contaminants. To establish total concentrations, parts of the same samples were extracted using an accelerated solvent extractor (ASE) with toluene at 100°C. The extracts were tested as inducers of AhR-dependent luciferase activity in the CALUX assay and for DNA breakage potential in the Comet bioassay. Results  The chemical analysis of the toluene extracts indicated slow degradation rates and the CALUX assay indicated high levels of AhR agonists in the same extracts. Compared to day 0, the bioavailable fractions showed no decrease in AhR agonist activity during the treatment but rather an up-going trend, which was supported by increasing levels of PAHs and an increased effect in the Comet bioassay after 274 days. The bio-TEQs calculated using the CALUX assay were higher than the TEQs calculated from chemical analysis in both extracts, indicating that there are additional toxic PAHs in both extracts that are not included in the chemically derived TEQ. Discussion  The response in the CALUX and the Comet bioassays as well as the chemical analysis indicate that the soil might be more toxic to organisms living in soil after 274 days of treatment than in the untreated soil, due to the release of previously sorbed PAHs and possibly also metabolic formation of novel toxicants. Conclusions  Our results put focus on the issue of slow degradation rates and bioavailability of PAHs during large-scale bioremediation treatments. The release of sorbed PAHs at the investigated PAH-contaminated site seemed to be faster than the degradation rate, which demonstrates the importance of considering the bioavailable fraction of contaminants during a bioremediation process. Recommendations and perspectives  It has to be ensured that soft remediation methods like biodegradation or the natural remediation approach do not result in the mobilization of toxic compounds including more mobile degradation products. For PAH-contaminated sites this cannot be assured merely by monitoring the 16 target PAHs. The combined use of a battery of biotests for different types of PAH effects such as the CALUX and the Comet assay together with bioavailability extraction methods may be a useful screening tool of bioremediation processes of PAH-contaminated soil and contribute to a more accurate risk assessment. If the bioremediation causes a release of bound PAHs that are left undegraded in an easily extracted fraction, the soil may be more toxic to organisms living in the soil as a result of the treatment. A prolonged treatment time may be one way to reduce the risk of remaining mobile PAHs. In critical cases, the remediation concept might have to be changed to ex situ remediation methods.     

Clonal differences in survival capacity, copper and zinc accumulation, and correlation with leaf polyamine levels in poplar: A large-scale field trial on heavily polluted soil

Three ex situ collections of poplar clones from natural populations of Populus alba and P. nigra growing in northern Italy were assessed for their genetic dissimilarity (GD) by means of amplified fragment length polymorphism (AFLP). The high GD evidenced within populations was exploited for screening 168 clones in a field trial on heavy metal-polluted soil. After one growth season, clonal differences in plant survival and growth were observed. On the basis of performance, six clones were singled out, and used to evaluate copper and zinc accumulation in different organs. Clonal differences in metal concentrations were most evident for leaves and stems; one clone of P. alba (AL35) had a distinctly higher concentration of both metals in the roots. Leaf polyamine (putrescine, spermidine, spermine) profiles correlated with tissue metal concentrations, depending on the clone, plant organ and metal. In particular, the high metal-accumulating clone AL35 exhibited a dramatically higher concentration of free and conjugated putrescine. Overall, the results indicate that, given the high GD of Populus even within populations, it is possible to identify genotypes best suited for soil clean-up, and useful also for investigating physiological markers associated with high metal accumulation/tolerance     

Population exposure and mortality due to regional background PM in Europe – Long-term simulations of source region and shipping contributions

This paper presents the contribution to population exposure (PE) of regional background fine primary (PPM_2.5) and secondary inorganic (SIA) particulate matter and its impact on mortality in Europe during 1997–2003 calculated with a chemistry transport model. Contributions to concentrations and PE due to emissions from shipping, Western (WEU), Eastern (EEU), and Northern Europe are compared.WEU contributes about 40% to both PPM_2.5 and SIA concentrations, whereas the EEU contribution to PPM_2.5 is much higher (43% of total PPM_2.5) than to SIA (29% of total SIA). The population weighted average concentration (PWC) of PPM_2.5 is a factor of 2.3 higher than average (non-weighted) concentrations, whereas for SIA the PWC is only a factor 1.6 higher. This is due to PPM_2.5 concentrations having larger gradients and being relatively high over densely populated areas, whereas SIA is formed outside populated areas. WEU emissions contribute relatively more than EEU to PWC and mortality due to both PPM_2.5 and SIA in Europe.The number of premature deaths in Europe is estimated to 301 000 per year due to PPM_2.5 exposure and 245 000 due to SIA, despite 3.3 times higher average SIA concentrations. This is due to population weighting and assumed (and uncertain) higher relative risk of mortality for PPM_2.5 components (2.8 times higher RR for PPM_2.5). This study indicates that it might be more efficient, for the health of the European population, to decrease primary PM emissions (especially in WEU) than to decrease precursors of SIA, but more knowledge on the toxicity of different PM constituents is needed before firm conclusions can be drawn.     

Levels of dioxins and furans in urban surface soil in Trondheim, Norway

A study was conducted on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in surface soil in order to determine the concentration levels and possibly distinguishing between known and potential sources. The concentration levels are low (0.16-14 ng I-TEQ kg(-1)). The results show a clear pattern where the highest concentration levels were found in the oldest parts of the city. A number of sources were recognised in the soil samples through congener profiles, not all of them active, although similar congener profiles make it extremely difficult to distinguish between different sources. Estimations show that the municipal solid waste incinerator (MSWI) and domestic wood burning are the largest PCDD/F pollution sources within the area.     

Comparison of techniques for estimating PAH bioavailability: uptake in Eisenia fetida, passive samplers and leaching using various solvents and additives

The aim of this study was to evaluate different techniques for assessing the availability of polycyclic aromatic hydrocarbons (PAHs) in soil. This was done by comparing the amounts (total and relative) taken up by the earthworm Eisenia fetida with the amounts extracted by solid-phase microextraction (SPME), semi-permeable membrane devices (SPMDs), leaching with various solvent mixtures, leaching using additives, and sequential leaching. Bioconcentration factors of PAHs in the earthworms based on equilibrium partitioning theory resulted in poor correlations to observed values. This was most notable for PAHs with high concentrations in the studied soil. Evaluation by principal component analysis (PCA) showed distinct differences between the evaluated techniques and, generally, there were larger proportions of carcinogenic PAHs (4-6 fused rings) in the earthworms. These results suggest that it may be difficult to develop a chemical method that is capable of mimicking biological uptake, and thus estimating the bioavailability of PAHs.