Reconciling Biodiversity Conservation and Widespread Deployment of Renewable Energy Technologies in the UK.

Renewable energy will potentially make an important contribution towards the dual aims of meeting carbon emission reduction targets and future energy demand. However, some technologies have considerable potential to impact on the biodiversity of the environments in which they are placed. In this study, an assessment was undertaken of the realistic deployment potential of a range of renewable energy technologies in the UK, considering constraints imposed by biodiversity conservation priorities. We focused on those energy sources that have the potential to make important energy contributions but which might conflict with biodiversity conservation objectives. These included field-scale solar, bioenergy crops, wind energy (both onshore and offshore), wave and tidal stream energy. The spatially-explicit analysis considered the potential opportunity available for each technology, at various levels of ecological risk. The resultant maps highlight the energy resource available, physical and policy constraints to deployment, and ecological sensitivity (based on the distribution of protected areas and sensitive species). If the technologies are restricted to areas which currently appear not to have significant ecological constraints, the total potential energy output from these energy sources was estimated to be in the region of 5,547 TWh/yr. This would be sufficient to meet projected energy demand in the UK, and help to achieve carbon reduction targets. However, we highlight two important caveats. First, further ecological monitoring and surveillance is required to improve understanding of wildlife distributions and therefore potential impacts of utilising these energy sources. This is likely to reduce the total energy available, especially at sea. Second, some of the technologies under investigation are currently not deployed commercially. Consequently this potential energy will only be available if continued effort is put into developing these energy sources/technologies, to enable realisation of their full potential.

Accumulation of microplastic on shorelines woldwide: sources and sinks.

Plastic debris <1 mm (defined here as microplastic) is accumulating in marine habitats. Ingestion of microplastic provides a potential pathway for the transfer of pollutants, monomers, and plastic-additives to organisms with uncertain consequences for their health. Here, we show that microplastic contaminates the shorelines at 18 sites worldwide representing six continents from the poles to the equator, with more material in densely populated areas, but no clear relationship between the abundance of miocroplastics and the mean size-distribution of natural particulates. An important source of microplastic appears to be through sewage contaminated by fibers from washing clothes. Forensic evaluation of microplastic from sediments showed that the proportions of polyester and acrylic fibers used in clothing resembled those found in habitats that receive sewage-discharges and sewage-effluent itself. Experiments sampling wastewater from domestic washing machines demonstrated that a single garment can produce >1900 fibers per wash. This suggests that a large proportion of microplastic fibers found in the marine environment may be derived from sewage as a consequence of washing of clothes. As the human population grows and people use more synthetic textiles, contamination of habitats and animals by microplastic is likely to increase.

Transport and release of chemicals from plastics to the environment and to wildlife.

Plastics debris in the marine environment, including resin pellets, fragments and microscopic plastic fragments, contain organic contaminants, including polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons, petroleum hydrocarbons, organochlorine pesticides (2,2'-bis(p-chlorophenyl)-1,1,1-trichloroethane, hexachlorinated hexanes), polybrominated diphenylethers, alkylphenols and bisphenol A, at concentrations from sub ng g(-1) to microg g(-1). Some of these compounds are added during plastics manufacture, while others adsorb from the surrounding seawater. Concentrations of hydrophobic contaminants adsorbed on plastics showed distinct spatial variations reflecting global pollution patterns. Model calculations and experimental observations consistently show that polyethylene accumulates more organic contaminants than other plastics such as polypropylene and polyvinyl chloride. Both a mathematical model using equilibrium partitioning and experimental data have demonstrated the transfer of contaminants from plastic to organisms. A feeding experiment indicated that PCBs could transfer from contaminated plastics to streaked shearwater chicks. Plasticizers, other plastics additives and constitutional monomers also present potential threats in terrestrial environments because they can leach from waste disposal sites into groundwater and/or surface waters. Leaching and degradation of plasticizers and polymers are complex phenomena dependent on environmental conditions in the landfill and the chemical properties of each additive. Bisphenol A concentrations in leachates from municipal waste disposal sites in tropical Asia ranged from sub microg l(-1) to mg l(-1) and were correlated with the level of economic development.

Expanding the range of halogenated 1'-methyl-1,2'-bipyrroles (MBPs) using GC/ECNI-MS and GCxGC/TOF-MS.

Halogenated 1'methyl-1,2'-bipyrroles (MBPs) have been identified worldwide in marine mammals. Here we present the tentative identification of previously undetected MBP congeners in Delpinus delphis blubber using gas chromatography/electron capture negative ion mass spectrometry (GC/ECNI-MS) and comprehensive two-dimensional gas chromatography/time of flight mass spectrometry (GCxGC/TOF-MS). This is the first report of 26 congeners. The presence of numerous partially halogenated congeners suggests that they are either biosynthesized concomitantly with their perhalogenated counterparts or that their dehalogenation products can also bioaccumulate. The newly found compounds fit the geographic trend that has been previously noted. That is, samples from the Atlantic Ocean are dominated by the more brominated congeners while those from the Pacific are dominated by the more chlorinated congeners.

Potential for plastics to transport hydrophobic contaminants.

Plastic debris litters marine and terrestrial habitats worldwide. It is ingested by numerous species of animals, causing deleterious physical effects. High concentrations of hydrophobic organic contaminants have also been measured on plastic debris collected from the environment, but the fate of these contaminants is poorly understood. Here, we examine the uptake and subsequent release of phenanthrene by three plastics. Equilibrium distribution coefficients for sorption of phenanthrene from seawater onto the plastics varied by more than an order of magnitude (polyethylene >> polypropylene > polyvinyl chloride (PVC)). In all cases, sorption to plastics greatly exceeded sorption to two natural sediments. Desorption rates of phenanthrene from the plastics or sediments back into solution spanned several orders of magnitude. As expected, desorption occurred more rapidly from the sediments than from the plastics. Using the equilibrium partitioning method, the effects of adding very small quantities of plastic with sorbed phenanthrene to sediment inhabited by the lugworm (Arenicola marina) were evaluated. We estimate that the addition of as little as 1 microg of contaminated polyethylene to a gram of sediment would give a significant increase in phenanthrene accumulation by A. marina. Thus, plastics may be important agents in the transport of hydrophobic contaminants to sediment-dwelling organisms.

Evaluation of gas chromatographic isotope fractionation and process contamination by carbon in compound-specific radiocarbon analysis.

The relevance of both modern and fossil carbon contamination as well as isotope fractionation during preparative gas chromatography for compound-specific radiocarbon analysis (CSRA) was evaluated. Two independent laboratories investigated the influence of modern carbon contamination in the sample cleanup procedure and preparative capillary gas chromatography (pcGC) of a radiocarbon-dead 3,3',4,4',5,5'-hexachlorobiphenyl (PCB 169) reference. The isolated samples were analyzed for their 14C/12C ratio by accelerator mass spectrometry. Sample Delta14C values of -996 +/- 20 and -985 +/- 20 per thousand agreed with a Delta14C of -995 +/- 20 per thousand for the unprocessed PCB 169, suggesting that no significant contamination by nonfossil carbon was introduced during the sample preparation process at either laboratory. A reference compound containing a modern 14C/12C ratio (vanillin) was employed to evaluate process contamination from fossil C. No negative bias due to fossil C was observed (sample Delta14C value of 165 +/- 20 per thousand agreed with Delta14C of 155 +/- 12 per thousand for the unprocessed vanillin). The extent of isotopic fractionation that can be induced during pcGC was evaluated by partially collecting the vanillin model compound of modern 14C/12C abundance. A significant change in the delta13C and delta14C values was observed when only parts of the eluting peak were collected (delta13C values ranged from -15.75 to -49.91 per thousand and delta14C values from -82.4 to +4.71 per thousand). Delta14C values, which are normalized to a delta13C of -25 per thousand, did not deviate significantly (-58.9 to -5.8 per thousand, considering the uncertainty of approximately +/-20 per thousand). This means that normalization of radiocarbon results to a delta13C of -25 per thousand, normally performed to remove effects of environmental isotope fractionation on 14C-based age determinations, also cor-rects sufficiently for putative isotopic fractionation that may occur during pcGC isolation of individual compounds for CSRA.

Halogenated organic compounds in archived whale oil: a pre-industrial record.

To provide additional evidence that several halogenated organic compounds (HOCs) found in environmental samples are natural and not industrially produced, we analyzed an archived whale oil sample collected in 1921 from the last voyage of the whaling ship Charles W. Morgan. This sample, which pre-dates large-scale industrial manufacture of HOCs, contained two methoxylated polybrominated diphenyl ethers (MeO-PBDEs), five halogenated methyl bipyrroles (MBPs), one halogenated dimethyl bipyrrole (DMBP), and tentatively one dimethoxylated polybrominated biphenyl (diMeO-PBB). This result indicates, at least in part, a natural source of the latter compounds.

Identification of highly brominated analogues of Q1 in marine mammals.

Three novel halogenated organic compounds (HOCs) have been identified in the blubber of marine mammals from coastal New England with the molecular formulae C(9)H(3)N(2)Br(6)Cl, C(9)H(3)N(2)Br(7), and C(9)H(4)N(2)Br(5)Cl. They were identified using high and low resolution gas chromatography mass spectrometry (GCMS) and appear to be highly brominated analogues of Q1, a heptachlorinated HOC suspected to be naturally produced. These compounds were found in Atlantic white sided dolphin (Lagenorhynchus acutus), bottlenose dolphin (Tursiops truncatus), common dolphin (Delphinus delphis), Risso's dolphin (Grampus griseus), harbor porpoise (Phocoena phocoena), beluga whale (Delphinapterus leucas), fin whale (Balaenoptera physalus), grey seal (Halichoerus grypus), harp seal (Phoca groenlandica) and a potential food source (Loligo pealei) with concentrations as high as 2.7 microg/g (lipid weight). The regiospecificity of C(9)H(3)N(2)Br(6)Cl is suggestive of a biogenic origin. Debromination of C(9)H(3)N(2)Br(6)Cl may be significant in the formation of C(9)H(4)N(2)Br(5)Cl.

Spectral characterization of two bioaccumulated methoxylated polybrominated diphenyl ethers.

Two methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were isolated from a True's beaked whale (Mesoplodon mirus) and identified by NMR (1H, 1H-1H and 1H-13C) and high resolution mass spectrometry as 2-(2',4'-dibromophenoxy)-3,5-dibromoanisole (6-MeO-BDE47) and 2-(2',4'-dibromophenoxy)-4,6-dibromoanisole (2'-MeO-BDE68). Previously the structures of these bioaccumulated compounds have been determined by comparison of their mass spectra and gas chromatographic (GC) retention times with those of authentic standards. While this method is accepted and generally successful, NMR of the isolated compounds allows us to definitively identify the congeners. Our characterizations are consistent with those made for MeO-PBDEs in other organisms, identified by chromatographic methods.

The mechanistic origin of regiochemical changes in the nitrosative N-dealkylation of N,N-dialkyl aromatic amines.

The regioselectivity of the nitrous acid mediated dealkylation of 4-substituted-N-ethyl-N-methylanilines is a function of the acidity of the reaction mixture. At high acidity deethylation predominates, whereas demethylation is the predominant reaction in nitrosamine formation at pH 2 and above. In some cases the regioselectivity of nitrosative dealkylation changes as the run proceeds. Through the use of the corresponding 4-nitroaniline as the primary substrate, CIDNP, kinetics, kinetic deuterium isotope effects and other transformations involving nitrosations with NO2 or NOBF4 in aprotic solvents, a new mechanism of tertiary amine nitrosation has been deduced and proposed to explain regioselective deethylation. The mechanism involves the oxidation of the substrate to the amine radical cation by NO+. This is followed by the abstraction of a hydrogen atom from the carbon adjacent to the amine nitrogen by NO2 to produce an iminium ion which reacts further to produce the corresponding aldehyde and the nitrosamine. Depending upon the acidity, this process competes with three other mechanistic pathways, two of which give the nitrosamine through the iminium ion, and one leads to the formation of C-nitro compounds. The competing pathways to nitrosamine formation involve NOH elimination from a nitrosammonium ion and deprotonation of the radical cation to give an alpha-amino radical which rapidly oxidized to the iminium ion. Predominant, but not highly regioselective demethylation occurs by these pathways. Nitro compound formation principally arises from the reaction of NO2 with the radical cation followed by deprotonation, but also occurs by para C-nitrosation followed by oxidation.

Two abundant bioaccumulated halogenated compounds are natural products.

Methoxylated polybrominated diphenyl ethers (MeO-PBDEs) have been found bioaccumulated in the tissues of a variety of aquatic animals and at concentrations comparable to those of anthropogenic halogenated organic compounds, including polychlorinated biphenyls (PCBs). The origin of the MeO-PBDEs has been uncertain; circumstantial evidence supports a natural and/or an industrial source. By analyzing the natural abundance radiocarbon content of two MeO-PBDEs isolated from a True's beaked whale (Mesoplodon mirus), we show that these compounds were naturally produced.