Generation and analysis of mixed chlorinated/brominated homologs of the halogenated natural product heptachloro-1'-methyl-1,2'-bipyrrole

The 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1, MBP-79) and further halogenated 1′-methyl-1,2′-bipyrroles (MBPs) are a class of marine natural products repeatedly detected in seafood and marine mammals from all over the world. Only Q1 is currently commercially available as reference standard and the full synthesis of mixed brominated-chlorinated compound is rather complicated. For this reason, synthetic Q1 (240 mg) was transferred into bromine-containing MBPs by UV-irradiation in the presence of bromine. Bromine, which rapidly vanished from the solutions, was re-newed during the reaction in order to generate higher amounts of Br-containing MBPs. A total of ∼150 mg Q1 was transferred after ∼10 min irradiation with high amounts of Br₂ to give 30.5 mg BrCl₆-MBPs along with lower proportions of Br₂Cl₅-, Br₃Cl₄-, Br₄Cl₃- and traces of Br₅Cl₂-MBPs. Longer UV-irradiation in the presence of Br₂ even allowed for the detection of Br₆Cl-MBPs and traces of Br₇-MBP. However, this reaction also provided some unknown by-products. A sample stored in the dark and later in in-door light (no UV irradiation) also eliminated Q1 after 76 d in favour of heptahalogenated MBPs with up to three bromine substituents. The irradiation products were separated on silica, and fractions containing only Q1 and BrCl₆-MBPs were then further fractionated by non-aqueous RP-HPLC. A pure isolate of the major BrCl₆-MBP (∼1.5 mg) was characterized by GC/MS and ¹³C NMR to be 2-bromo-3,3′,4,4′,5,5′-hexachloro-1-methyl-1,2′-bipyrrole (Br-MBP-75). Partial GC enantioseparation of the axially chiral Br-MBP-75 was achieved on a β-PMCD column. A full enantioseparation was managed by enantioselective HPLC using a NUCLEOCEL DELTA S column. Low amounts of pure BrCl₆-MBP enantiomers could be trapped.     

Evaluating approaches for scaling-up community-based marine-protected areas into socially equitable and ecologically representative networks

Marine-protected areas (MPAs) are vital to marine conservation, but their coverage and distribution is insufficient to address declines in global biodiversity and fisheries. In response, many countries have committed through the Aichi Target 11 of the Convention on Biological Diversity to conserve 10% of the marine environment through ecologically representative and equitably managed MPAs by 2020. The rush to fulfill this commitment has raised concerns on how increasing MPA coverage will affect other elements of Target 11, including representation and equity. We examined a Philippines case study to assess and compare 3 MPA planning approaches for biodiversity representation and equitable distribution of costs to small-scale fishers. In the opportunistic approach, MPAs were identified and supported by coastal communities. The donor-assisted approach used local knowledge to select MPAs through a national-scale and donor-assisted conservation project. The systematic conservation planning approach identified MPA locations with the spatial prioritization software Marxan with Zones to achieve biodiversity objectives with minimal costs to fishers. We collected spatial data on biodiversity and fisheries features and performed a gap analysis to evaluate MPAs derived from different approaches. We assessed representation based on the proportion of biodiversity features conserved in MPAs and distribution equity by the distribution of opportunity costs (fishing areas lost in MPAs) among fisher stakeholder groups. The opportunistic approach did not ineffectively represent biodiversity and resulted in inequitable costs to fishers. The donor-assisted approach affected fishers disproportionately but provided near-optimal regional representation. Only the systematic approach achieved all representation targets with minimal and equitable costs to fishers. Our results demonstrate the utility of systematic conservation planning to address key elements of Target 11 and highlight opportunities (e.g., integration of local and scientific knowledge can address representation and equity concerns) and pitfalls (e.g., insufficient stakeholder considerations can exacerbate social inequalities) for planning MPAs in similar contexts.     

Glass sponges arrest pumping in response to sediment: implications for the physiology of the hexactinellid conduction system

The hexactinellid sponge Rhabdocalyptus dawsoni propagates electrical signals to arrest its feeding current in response to mechanical stimuli and sediment. The deepwater habitat of other species of glass sponge, and the difficulty of working with the tissue in vitro have so far prevented confirmation of electrical signaling in other members of the Class. Here we show in laboratory experiments (ex situ) that mechanical and sediment stimuli trigger immediate arrest in R. dawsoni and in a second species of hexactinellid, Aphrocallistes vastus, suggesting that rapid signaling may be a general feature of glass sponge tissue. Further, responses of the two species differed, suggestive of underlying physiological differences in the conduction system. R. dawsoni and A. vastus were sensitive to sediment but arrests were often prolonged in R. dawsoni, whereas in A. vastus pumping resumed immediately following each arrest. Fine sediment (<25 μm) caused immediate arrests in R. dawsoni and A. vastus, but with a higher stimulus threshold in A. vastus. Large amounts of sediment triggered repeated arrests in both species, and prolonged exposure to sediment (over 4 h) caused a gradual reduction in pumping, with recovery taking up to 25 h. During recovery, both species of sponge carried out repeated arrests, which had a precise periodicity indicative of pacemaker activity. Scanning electron microscopy of the tissue of these specimens showed many chambers were clogged. The results suggest that the glass sponge conduction system generates arrest of the feeding current that prevent uptake of small amounts of sediment, and that each species has different threshold sensitivities. However, ongoing exposure to sediment can clog the filtration apparatus.     

Arsenic, cadmium, and lead in California cropland soils: role of phosphate and micronutrient fertilizers

Phosphate and micronutrient fertilizers contain potentially harmful trace elements, such as arsenic (As), cadmium (Cd), and lead (Pb). We investigated if application of these fertilizer increases the As, Cd, and Pb concentrations of the receiving soils. More than 1000 soil samples were collected in seven major vegetable production regions across California. Benchmark soils (no or low fertilizer input) sampled in 1967 and re-sampled in 2001 served as a baseline. Soils were analyzed for total concentrations of As, Cd, Pb, P, and Zn. The P and Zn concentrations of the soils were indicators of P fertilizer and micronutrient inputs, respectively. Results showed that the concentrations of these elements in the vegetable production fields in some production areas of California had been shifted upward. Principal component analysis and cluster analysis showed that the seven production areas could be sorted into three categories: (i) enrichment of As, Cd, and Pb, which was associated with the enrichment of P and Zn in one of the seven areas surveyed; (ii) enrichment of As, which was associated with enrichment of Zn in two of the seven areas surveyed; and (iii) no remarkable correlation between enrichment of As, Cd, and Pb and enrichment of P and Zn in the other four areas surveyed.     

Stable carbon isotope analysis (δ13C values) of polybrominated diphenyl ethers and their UV-transformation products

Polybrominated diphenyl ethers (PBDEs) are frequently detected in food and environmental samples. We used compound specific isotope analysis to determine the δ¹³C values of individual PBDEs in two technical mixtures. Within the same technical product (DE-71 or DE-79), BDE congeners were the more depleted in ¹³C the higher brominated they were. In contrast, the products of light-induced hydrodebromination of BDE 47 and technical DE-79 were more enriched in ¹³C because of more stable bonds between ¹³C and bromine. As a result, the δ¹³C values of the irradiated solution progressed diametrically compared to those of the technical synthesis. The ratio of the δ¹³C values of BDE 47 to BDE 99 and of BDE 99 to BDE 153 are thus suggested as indicators to distinguish native technical products from transformation products. Ratios <1 are typical for native congeners (e.g. in DE-71) while the reversed ratio (>1) is typical of transformation products.     

Response of sugar maple to calcium addition to northern hardwood forest

Watershed budget studies at the Hubbard Brook Experimental Forest (HBEF), New Hampshire, USA, have demonstrated high calcium depletion of soil during the 20th century due, in part, to acid deposition. Over the past 25 years, tree growth (especially for sugar maple) has declined on the experimental watersheds at the HBEF. In October 1999, 0.85 Mg Ca/ha was added to Watershed 1 (W1) at the HBEF in the form of wollastonite (CaSiO3), a treatment that, by summer 2002, had raised the pH in the Oie horizon from 3.8 to 5.0 and, in the Oa horizon, from 3.9 to 4.2. We measured the response of sugar maple to the calcium fertilization treatment on W1. Foliar calcium concentration of canopy sugar maples in W1 increased markedly beginning the second year after treatment, and foliar manganese declined in years four and five. By 2005, the crown condition of sugar maple was much healthier in the treated watershed as compared with the untreated reference watershed (W6). Following high seed production in 2000 and 2002, the density of sugar maple seedlings increased significantly on W1 in comparison with W6 in 2001 and 2003. Survivorship of the 2003 cohort through July 2005 was much higher on W1 (36.6%) than W6 (10.2%). In 2003, sugar maple germinants on W1 were approximately 50% larger than those in reference plots, and foliar chlorophyll concentrations were significantly greater (0.27 g/m2 vs. 0.23 g/m2 leaf area). Foliage and fine-root calcium concentrations were roughly twice as high, and manganese concentrations twice as low in the treated than the reference seedlings in 2003 and 2004. Mycorrhizal colonization of seedlings was also much greater in the treated (22.4% of root length) than the reference sites (4.4%). A similar, though less dramatic, difference was observed for mycorrhizal colonization of mature sugar maples (56% vs. 35%). These results reinforce and extend other regional observations that sugar maple decline in the northeastern United States and southern Canada is caused in part by anthropogenic effects on soil calcium status, but the causal interactions among inorganic nutrition, physiological stress, mycorrhizal colonization, and seedling growth and health remain to be established.     

Visitor perceptions of rural landscapes: a case study in the Peak District National Park, England

Maintaining national parks is an integral policy tool to conserve rare habitats. However, because national parks are funded by taxpayers, they must also serve the needs of the general public. Increasingly, and thanks to today's diverse society, there is evidence that this creates challenges for park managers who are pulled in two opposing directions: to conserve nature on the one hand and to meet different visitor expectations on the other. This tension was explored in the Peak District National Park, a rural landscape dominated by heather moorland and sheep farming in Northern England where research was conducted to determine how social class and ethnicity shaped perceptions of the park. Results uncovered that social class played a very strong role in shaping perceptions of this region with 'middle class' respondents reacting far more favourably to the park than people from more working class backgrounds. We observed ethnicity playing a similar role, though our results are less significantly different.     

Sources and Delivery of Nutrients to the Northwestern Gulf of Mexico from Streams in the South‐Central United States1

Rebich, Richard A., Natalie A. Houston, Scott V. Mize, Daniel K. Pearson, Patricia B. Ging, and C. Evan Hornig, 2011. Sources and Delivery of Nutrients to the Northwestern Gulf of Mexico From Streams in the South‐Central United States. Journal of the American Water Resources Association (JAWRA) 47(5):1061‐1086. DOI: 10.1111/j.1752‐1688.2011.00583.x Abstract: SPAtially Referenced Regressions On Watershed attributes (SPARROW) models were developed to estimate nutrient inputs [total nitrogen (TN) and total phosphorus (TP)] to the northwestern part of the Gulf of Mexico from streams in the South‐Central United States (U.S.). This area included drainages of the Lower Mississippi, Arkansas‐White‐Red, and Texas‐Gulf hydrologic regions. The models were standardized to reflect nutrient sources and stream conditions during 2002. Model predictions of nutrient loads (mass per time) and yields (mass per area per time) generally were greatest in streams in the eastern part of the region and along reaches near the Texas and Louisiana shoreline. The Mississippi River and Atchafalaya River watersheds, which drain nearly two‐thirds of the conterminous U.S., delivered the largest nutrient loads to the Gulf of Mexico, as expected. However, the three largest delivered TN yields were from the Trinity River/Galveston Bay, Calcasieu River, and Aransas River watersheds, while the three largest delivered TP yields were from the Calcasieu River, Mermentau River, and Trinity River/Galveston Bay watersheds. Model output indicated that the three largest sources of nitrogen from the region were atmospheric deposition (42%), commercial fertilizer (20%), and livestock manure (unconfined, 17%). The three largest sources of phosphorus were commercial fertilizer (28%), urban runoff (23%), and livestock manure (confined and unconfined, 23%).     

Incorporating effectiveness of community-based management in a national marine gap analysis for Fiji

Every action in a conservation plan has a different level of effect and consequently contributes differentially to conservation. We examined how several community-based, marine, management actions differed in their contribution to national-level conservation goals in Fiji. We held a workshop with experts on local fauna and flora and local marine management actions to translate conservation goals developed by the national government into ecosystem-specific quantitative objectives and to estimate the relative effectiveness of Fiji's community-based management actions in achieving these objectives. The national conservation objectives were to effectively manage 30% of the nation's fringing reefs, nonfringing reefs, mangroves, and intertidal ecosystems (30% objective) and 10% of other benthic ecosystems (10% objective). The experts evaluated the contribution of the various management actions toward national objectives. Scores ranged from 0 (ineffective) to 1 (maximum effectiveness) and included the following management actions: permanent closures (i.e., all extractive use of resources prohibited indefinitely) (score of 1); conditional closures harvested once per year or less as dictated by a management plan (0.50-0.95); conditional closures harvested without predetermined frequency or duration (0.10-0.85); other management actions, such as regulations on gear and species harvested (0.15-0.50). Through 3 gap analyses, we assessed whether the conservation objectives in Fiji had been achieved. Each analysis was based on a different assumption: (1) all parts of locally managed marine areas (including closures and other management) conserve species and ecosystems effectively; (2) closures conserve species and ecosystems, whereas areas outside closures, open to varying levels of resource extraction, do not; and (3) actions that allow different levels of resource extraction vary in their ability to conserve species and ecosystems. Under assumption 1, Fiji's national conservation objectives were exceeded in all marine ecosystems; under assumption 2, none of Fiji's conservation objectives were met; and under assumption 3, on the basis of the scores assigned by experts, Fiji achieved the 10% but not the 30% objectives for ecosystems. Understanding the relative contribution of management actions to achieving conservation objectives is critical in the assessment of conservation achievements at the national level, where multiple management actions will be needed to achieve national conservation objectives.