Synthesis and tentative identification of novel polybrominated diphenyl ether metabolites in human blood

Hydroxylated polybrominated diphenyl ethers (OH-PDBEs) are exogenous, bioactive compounds that originate, to a large extent, from anthropogenic activities, although they are also naturally produced in the environment. In the present study nine new authentic OH-PBDE reference standards and their corresponding methyl ether derivatives (MeO-PBDEs) were synthesised and characterised by NMR spectroscopy and mass spectrometry. Seven of the authentic reference standards prepared were thereafter tentatively identified in a pooled human blood sample. The tentatively identified OH-PBDEs were 3-hydroxy-2,2',4,4',6-pentabromodiphenyl ether, 3'-hydroxy-2,2',4,4',6-pentabromodiphenyl ether, 3-hydroxy-2,2',4,4',5-pentabromodiphenyl ether, 3-hydroxy-2,2',4,4',5,6'-hexabromodiphenyl ether, 3'-hydroxy-2,2',4,4',5,6'-hexabromodiphenyl ether, 3-hydroxy-2,2',4,4',5,5'-hexabromodiphenyl ether and 4-hydroxy-2,2',3,4',5,5',6-heptabromodiphenyl ether. An additional seven OH-PBDEs were tentatively identified in the pooled human blood sample, of which one OH-PBDE, 4'-hydroxy-2,2',4,5,5'-pentabromodiphenyl ether, has not been identified in human blood before. The identification was performed using gas chromatography-mass spectrometry (GC-MS) recording the bromine ions m/z 79, 81. The tentative identification was supported by the peaks relative retention times (RRTs) compared to authentic references on two GC columns of different polarities for the hexa-, and heptabrominated OH-PBDEs, and three different GC columns for the pentabrominated OH-PBDEs. The OH-PBDE congeners most likely originate from human metabolism of a flame retardant, i.e. polybrominated diphenyl ethers (PBDEs), due to the relatively high concentrations of PBDEs in the same human blood sample and the fact that these PBDEs could form the tentatively identified OH-PBDEs via metabolic direct hydroxylation or via 1,2-shift.     

Regional patterns and controls of biomass in semiarid woodlands: lessons from the Northern Argentina Dry Chaco

Land use change, particularly in forested ecosystems, has a direct impact on the global carbon cycle. Consequently, the regional assessment of biomass and the understanding of its current spatial controls are research priorities for regional ecology and land use. Field data and satellite imagery were combined here to map woodlands and estimate their above-ground biomass (AGB) in the Dry Chaco ecoregion of northern Argentina. Allometric equations were used to derive AGB from diameter at breast height data collected at 50 samples during 2007. In order to generate the AGB regional map, this information was later associated with MODIS-Terra spectral data (NDVI) using the Random Forest (RF) method. Finally, AGB spatial patterns were associated with potential biophysical and human controlling factors through correlation and regression analyses. Results indicate that the use of RF and NDVI of the dry season derived from MODIS-Terra was suitable to map regional AGB, what makes this methodology applicable to other dry woodlands. The RF model used to map AGB showed a mean deviation of 2.9 % and a precision of 15 % for one prediction. At this regional scale of analysis, biophysical rather than human factors controlled AGB spatial patterns, in part because the region includes a wide range of environmental situations. Warmer conditions showed a higher biomass, suggesting an energetic limitation for AGB accumulation. However, human controls (distance to towns, cultivation, and roads) also conditioned AGB patterns, suggesting lower AGB values near cultivated areas. The relation between AGB and water availability was surprisingly weak, but partially obscured by the land use history and degradation due to extensive cattle ranching. We propose that a combination of environmental factor and land use affects the AGB regional patterns and promotes unexpected relationships with environmental factors. This work represents the first spatially explicit AGB (patterns and controls) analysis for an extensive subtropical dry woodland area (113,000 km²) and shows how biophysical and human factors co-control regional patterns.     

Financing remediation by delisting and selling clean portions of affected property

It is an established fact that property owners can face significant liabilities as a result of an on-site environmental contamination problem. This paper outlines a successful, innovative remedial strategy that, in conjunction with agency negotiation, afforded a property owner minimal financial expenditure and, at the same time, facilitated property cleanup and reuse. The strategy includes the delisting and sale of “clean” portions of the property to obtain the finances necessary to remediate the remaining “impacted” portion of the property. Previous investigations performed by EPA indicate the affected area to be a five to seven acre area located in the northeast portion of the property. Since a portion of the property was affected, significant restrictions for long-term use were placed on the entire property. A summary of environmental data generated for the property was prepared and submitted to the agency. This data summary communicated a strategy which was developed to delist and sell the “clean” portion of the property and to use the proceeds to clean up the affected property. To accomplish this, several tasks were outlined, including work-plan preparation and submittal, data collection, and interim remedial activities. In addition, a risk assessment is planned to identify potential threats to receptors downgradient of the impacted areas. This strategy allows the owner of an environmentally distressed property to use financial assets of the property to facilitate an acceptable solution with both regulatory agencies and the surrounding community.     

Linking local to global properties in branching modular networks: gorgonian coral colonies

Branching growth is present both in plants and animals, either marine or terrestrial. Although cellular and other modular levels of organization in plants and animals have evolved through different molecular and physiological mechanisms, several aspects of their branching modular system and morphology are similar. We studied vessel organization and colony integration, in order to comprehend underlying relationships between different structural components in a gorgonian coral network. The theoretical formalism was validated in the gorgonian coral Eunicea mammosa (Plexauridae, Octocorallia) in Belize. As in vascular plants, these colonial animals create a complex network of connections among modular branches integrated in stem canals downstream toward the base. A new formalism is proposed for describing gorgonian branching. A global property of a colony is for instance the size of its base or its weight whereas a local property is the size of branch in a particular place of the colony. However, a global property is not the simple addition of local modular properties, as the case of stem canals in the colony base. Theoretically, the process of branching is tightly intertwined with the internal network organization. The colony network centralization is driven by a linear relationship between the total number of branches and the stem canals at the base of the colony. If stem canals play important roles in the transport of nutrients throughout the colony and the biomechanical support from the base up to the tips, we can assume that there is an underlying association between the number of stem canals at the base and the number of for example, terminal branches. These associations may provide new findings that extend our understanding of the functional organization of tree-like networks in octocorals and their vascular systems. The idea that the external components of a tree-like plant network are directly correlated and connected down to the main trunk seems to be analogous in an animal system.