Trace me if you can: the use of intrinsic biogeochemical markers in marine top predators

Human activities have serious impacts on marine apex predators. Inadequate knowledge of the spatial and trophic ecology of these marine animals ultimately compromises the viability of their populations and impedes our ability to use them as environmental biomonitors. Intrinsic biogeochemical markers, such as stable isotopes, fatty acids, trace elements, and chemical pollutants, are increasingly being used to trace the spatial and trophic ecology of marine top predators. Notable advances include the emergence of the first oceanographic"isoscapes" (isotopic geographic gradients), the advent of compound-specific isotopic analyses, improvements in diet reconstruction through Bayesian statistics, and tissue analysis of tracked animals to ground-truth biogeochemical profiles. However, most researchers still focus on only a few tracers. Moreover, insufficient knowledge of the biogeochemical integration in tissues, fractionation and routing processes, and geographic and temporal variability in baseline levels continue to hamper the resolution and potential of these markers in studying the spatial and feeding ecology of top predators.

Longer and less overlapping food webs in anthropogenically disturbed marine ecosystems: confirmations from the past

The human exploitation of marine resources is characterised by the preferential removal of the largest species. Although this is expected to modify the structure of food webs, we have a relatively poor understanding of the potential consequences of such alteration. Here, we take advantage of a collection of ancient consumer tissues, using stable isotope analysis and SIBER to assess changes in the structure of coastal marine food webs in the South-western Atlantic through the second half of the Holocene as a result of the sequential exploitation of marine resources by hunter-gatherers, western sealers and modern fishermen. Samples were collected from shell middens and museums. Shells of both modern and archaeological intertidal herbivorous molluscs were used to reconstruct changes in the stable isotopic baseline, while modern and archaeological bones of the South American sea lion Otaria flavescens, South American fur seal Arctocephalus australis and Magellanic penguin Spheniscus magellanicus were used to analyse changes in the structure of the community of top predators. We found that ancient food webs were shorter, more redundant and more overlapping than current ones, both in northern-central Patagonia and southern Patagonia. These surprising results may be best explained by the huge impact of western sealing on pinnipeds during the fur trade period, rather than the impact of fishing on fish populations. As a consequence, the populations of pinnipeds at the end of the sealing period were likely well below the ecosystem's carrying capacity, which resulted in a release of intraspecific competition and a shift towards larger and higher trophic level prey. This in turn led to longer and less overlapping food webs.

Metals and Selenium as bioindicators of geographic and trophic segregation in Giant Petrels Macronectes spp.

We analysed concentrations of cadmium, lead, mercury and selenium in blood from males and females of the 2 sibling species of giant petrels, the northern Macronectes halli and the southern M. giganteus, breeding sympatrically at Bird Island (South Georgia, Antarctica). Blood samples were collected in 1998 during the incubation period, from 5 November to 10 December. Between species, cadmium and lead concentrations were significantly higher for northern than for southern giant petrels, which probably resulted from northern giant petrels wintering in more polluted areas (mainly on the Patagonian Shelf and Falkland Islands) compared to southern giant petrels (wintering mainly around South Georgia and the South Sandwich Islands). Between sexes, cadmium concentrations were significantly higher for females than for males in both species, corresponding to the more pelagic habits of females compared to the more scavenging habits of males. Lead and cadmium concentrations in circulating blood decreased significantly over the incubation period, suggesting that when breeding at Bird Island, exposure to the source of pollution had ended, and these metals had been cleared from the blood and excreted, or rapidly transferred to other tissues. Association of lead and cadmium with a common source of pollution was further corroborated by a significant positive correlation between the levels of the 2 elements found. Mercury levels were similar between the species, but showed an opposite trend between sexes, with males showing higher levels than females in northern giant petrels, and the opposite was true in southern giant petrels, with no changes throughout incubation. Selenium levels were similar between sexes, but significantly greater for northern than for southern giant petrels. Moreover, there was a significant increase in the selenium levels over the incubation period in northern giant petrels. Age of adult birds did not affect metal concentrations. Coefficients of variation of metal levels were consistently lower for northern than for southern giant petrels, particularly for mercury, suggesting that the former species is more dietary specialised than the latter. Contaminant analyses, when combined with accurate information on seabird movements, obtained through geolocation or satellite tracking, help us to understand geographic variation of pollution in the marine environment.

Synthesis and structure - Activity relationship study of potent cytotoxic analogues of the marine alkaloid Lamellarin D

The marine alkaloid, Lamellarin D (Lam-D), has shown potent cytotoxicity in numerous cancer cell lines, and was recently identified as a potent topoisomerase I inhibitor. A library of open lactone analogs of Lam-D was prepared from a methyl 5,6-dihydropyrrolo[2,1-a]isoquinoline-3- carboxylate scaffold (1) by introducing various aryl groups through sequential and regioselective bromination, followed by Pd(0)-catalyzed Suzuki cross-coupling chemistry. The compounds were obtained in a 24-44% overall yield, and tested in a panel of three human tumor cell lines, MDA-MB- 231 (breast), A-549 (lung), and HT-29 (colon), to evaluate their cytotoxic potential. From these data the SAR study concluded that more than 75% of the open-chain Lam-D analogs tested showed cytotoxicity in a low micromolar GI50 range.

Synthesis and structure - Activity relationship study of potent cytotoxic analogues of the marine alkaloid Lamellarin D

The marine alkaloid, Lamellarin D (Lam-D), has shown potent cytotoxicity in numerous cancer cell lines, and was recently identified as a potent topoisomerase I inhibitor. A library of open lactone analogs of Lam-D was prepared from a methyl 5,6-dihydropyrrolo[2,1-a]isoquinoline-3- carboxylate scaffold (1) by introducing various aryl groups through sequential and regioselective bromination, followed by Pd(0)-catalyzed Suzuki cross-coupling chemistry. The compounds were obtained in a 24-44% overall yield, and tested in a panel of three human tumor cell lines, MDA-MB- 231 (breast), A-549 (lung), and HT-29 (colon), to evaluate their cytotoxic potential. From these data the SAR study concluded that more than 75% of the open-chain Lam-D analogs tested showed cytotoxicity in a low micromolar GI50 range.

Externalities of Shipping in the Gulf of Finland until 2015

During the last few years, the discussion on the marginal social costs of transportation has been active. Applying the externalities as a tool to control transport would fulfil the polluter pays principle and simultaneously create a fair control method between the transport modes. This report presents the results of two calculation algorithms developed to estimate the marginal social costs based on the externalities of air pollution. The first algorithm calculates the future scenarios of sea transport traffic externalities until 2015 in the Gulf of Finland. The second algorithm calculates the externalities of Russian passenger car transit traffic via Finland by taking into account both sea and road transport. The algorithm estimates the ship-originated emissions of carbon dioxide (CO₂), nitrogen oxides (NO_x), sulphur oxides (SO_x), particulates (PM) and the externalities for each year from 2007 to 2015. The total NOx emissions in the Gulf of Finland from the six ship types were almost 75.7 kilotons (Table 5.2) in 2007. The ship types are: passenger (including cruisers and ROPAX vessels), tanker, general cargo, Ro-Ro, container and bulk vessels. Due to the increase of traffic, the estimation for NO_x emissions for 2015 is 112 kilotons. The NO_x emission estimation for the whole Baltic Sea shipping is 370 kilotons in 2006 (Stipa & al, 2007). The total marginal social costs due to ship-originated CO₂, NO_x, SO_x and PM emissions in the GOF were calculated to almost 175 million Euros in 2007. The costs will increase to nearly 214 million Euros in 2015 due to the traffic growth. The major part of the externalities is due to CO₂ emissions. If we neglect the CO2 emissions by extracting the CO₂ externalities from the results, we get the total externalities of 57 million Euros in 2007. After eight years (2015), the externalities would be 28 % lower, 41 million Euros (Table 8.1). This is the result of the sulphur emissions reducing regulation of marine fuels. The majority of the new car transit goes through Finland to Russia due to the lack of port capacity in Russia. The amount of cars was 339 620 vehicles (Statistics of Finnish Customs 2008) in 2005. The externalities are calculated for the transportation of passenger vehicles as follows: by ship to a Finnish port and, after that, by trucks to the Russian border checkpoint. The externalities are between 2 – 3 million Euros (year 2000 cost level) for each route. The ports included in the calculations are Hamina, Hanko, Kotka and Turku. With the Euro-3 standard trucks, the port of Hanko would be the best choice to transport the vehicles. This is because of lower emissions by new trucks and the saved transport distance of a ship. If the trucks are more polluting Euro 1 level trucks, the port of Kotka would be the best choice. This indicates that the truck emissions have a considerable effect on the externalities and that the transportation of light cargo, such as passenger cars by ship, produces considerably high emission externalities. The emission externalities approach offers a new insight for valuing the multiple traffic modes. However, the calculation of the marginal social costs based on the air emission externalities should not be regarded as a ready-made calculation system. The system is clearly in the need of some improvement but it can already be considered as a potential tool for political decision making.

Calcium phosphate biomaterials from marine algae. Hydrothermal synthesis and characterisation

Calcium phosphate compounds such as Hydroxyapatite (HAp) were prepared by hydrothermal synthesis with phycogenic CaCO3 as starting material. Material obtained was characterised by usual methods (XRD, FTIR, TG, N2-adsorption, SEM and EDX) in order to study its physical-chemical characteristics. The prepared HAp showed that it may be suitable for use as a biomaterial.

Geographic patterns of genetic variation in a broadly distributed marine vertebrate: new insights into loggerhead turtle stock structure from expanded mitochondrial DNA sequences

Previous genetic studies have demonstrated that natal homing shapes the stock structure of marine turtle nesting populations. However, widespread sharing of common haplotypes based on short segments of the mitochondrial control region often limits resolution of the demographic connectivity of populations. Recent studies employing longer control region sequences to resolve haplotype sharing have focused on regional assessments of genetic structure and phylogeography. Here we synthesize available control region sequences for loggerhead turtles from the Mediterranean Sea, Atlantic, and western Indian Ocean basins. These data represent six of the nine globally significant regional management units (RMUs) for the species and include novel sequence data from Brazil, Cape Verde, South Africa and Oman. Genetic tests of differentiation among 42 rookeries represented by short sequences (380 bp haplotypes from 3,486 samples) and 40 rookeries represented by long sequences (~800 bp haplotypes from 3,434 samples) supported the distinction of the six RMUs analyzed as well as recognition of at least 18 demographically independent management units (MUs) with respect to female natal homing. A total of 59 haplotypes were resolved. These haplotypes belonged to two highly divergent global lineages, with haplogroup I represented primarily by CC-A1, CC-A4, and CC-A11 variants and haplogroup II represented by CC-A2 and derived variants. Geographic distribution patterns of haplogroup II haplotypes and the nested position of CC-A11.6 from Oman among the Atlantic haplotypes invoke recent colonization of the Indian Ocean from the Atlantic for both global lineages. The haplotypes we confirmed for western Indian Ocean RMUs allow reinterpretation of previous mixed stock analysis and further suggest that contemporary migratory connectivity between the Indian and Atlantic Oceans occurs on a broader scale than previously hypothesized. This study represents a valuable model for conducting comprehensive international cooperative data management and research in marine ecology.

The Andean Biotic Index (ABI): revised tolerance to pollution values for macroinvertebrate families and index performance evaluation.

Score-based biotic indices are widely used to evaluate the water quality of streams and rivers. Few adaptations of these indices have been done for South America because there is a lack of knowledge on mac-roinvertebrate taxonomy, distribution and tolerance to pollution in the region. Several areas in the Andes are densely populated and there is need for methods to assess the impact of increasing human pressures on aquatic ecosystems. Considering the unique ecological and geographical features of the Andes, macroinvertebrate indices used in other regions must be adapted with caution. Here we present a review of the literature on mac-roinvertebrate distribution and tolerance to pollution in Andean areas above 2 000masl. Using these data, we propose an Andean Biotic Index (ABI), which is based on the BMWP index. In general, ABI includes fewer macroinvertebrate families than in other regions of the world where the BMWP index has been applied because altitude restricts the distribution of several families. Our review shows that in the high Andes, the tolerance of several macroinvertebrate families to pollution differs from those reported in other areas. We tested the ABI index in two basins in Ecuador and Peru, and compared it to other BMWP adaptations using the reference condi-tion approach. The ABI index is extremely useful for detecting the general impairment of rivers but class quality boundaries should be defined independently for each basin because reference conditions may be different. The ABI is widely used in Ecuador and Peru, with high correlations with land-use pressures in several studies. The ABI index is an integral part of the new multimetric index designed for high Andean streams (IMEERA). Rev. Biol. Trop. 62 (Suppl. 2): 249-273. Epub 2014 April 01.

Effects of artisanal fisheries on the scorpaenids (Scorpaena spp.) reproduction in the marine protected area of Cap de Creus (NW Mediterranean)

Rockfish species are considered important to the ecology of rocky-reef communities which constitute a key habitat in many coastal marine protected areas (MPAs). These species, which are commercially valuable for artisanal fisheries in the Mediterranean, display particular biological traits that could render them vulnerable to fishing. In this study we monitored the artisanal fisheries of scorpaenids (Scorpaena spp.) in the MPA of Cap de Creus (northwestern Mediterranean) in order to estimate the status of their populations, to link captures with the reproduction of these species, and to evaluate the potential impact that artisanal fishing may have on them. Data from onboard sampling with artisanal fishermen and from fisheries statistics (total landings) were used. Total landings and catch per unit of effort (CPUE) follow a clearly seasonal cycle, with a prominent peak during the summer months coinciding with their spawning season, which may be due to mating behavior prior to fertilization. Although maximum sizes are bigger inside the MPA than in non-protected areas situated close by, a significant percentage of individuals caught inside the MPA are below their size at sexual maturity. Although rockfish seem to be favored by the partial protection of the MPA, the allowed artisanal fisheries are probably impacting the reproduction of these species

Case-Crossover Analysis of Air Pollution Health Effects: A Systematic Review of Methodology and Application

Case-crossover is one of the most used designs for analyzing the health-related effects of air pollution. Nevertheless, no one has reviewed its application and methodology in this context. Objective: We conducted a systematic review of case-crossover (CCO) designs used to study the relationship between air pollution and morbidity and mortality, from the standpoint of methodology and application.Data sources and extraction: A search was made of the MEDLINE and EMBASE databases.Reports were classified as methodologic or applied. From the latter, the following information was extracted: author, study location, year, type of population (general or patients), dependent variable(s), independent variable(s), type of CCO design, and whether effect modification was analyzed for variables at the individual level. Data synthesis: The review covered 105 reports that fulfilled the inclusion criteria. Of these, 24 addressed methodological aspects, and the remainder involved the design’s application. In the methodological reports, the designs that yielded the best results in simulation were symmetric bidirectional CCO and time-stratified CCO. Furthermore, we observed an increase across time in the use of certain CCO designs, mainly symmetric bidirectional and time-stratified CCO. The dependent variables most frequently analyzed were those relating to hospital morbidity; the pollutants most often studied were those linked to particulate matter. Among the CCO-application reports, 13.6% studied effect modification for variables at the individual level.Conclusions: The use of CCO designs has undergone considerable growth; the most widely used designs were those that yielded better results in simulation studies: symmetric bidirectional and time-stratified CCO. However, the advantages of CCO as a method of analysis of variables at the individual level are put to little use

Association between Long-Term Exposure to Traffic-Related Air Pollution and Subclinical Atherosclerosis: The REGICOR Study

Background: Epidemiological evidence of the effects of long-term exposure to air pollu tion on the chronic processes of athero genesis is limited. Objective: We investigated the association of long-term exposure to traffic-related air pollu tion with subclinical atherosclerosis, measured by carotid intima media thickness (IMT) and ankle–brachial index (ABI). Methods: We performed a cross-sectional analysis using data collected during the reexamination (2007–2010) of 2,780 participants in the REGICOR (Registre Gironí del Cor: the Gerona Heart Register) study, a population-based prospective cohort in Girona, Spain. Long-term exposure across residences was calculated as the last 10 years’ time-weighted average of residential nitrogen dioxide (NO2) estimates (based on a local-scale land-use regression model), traffic intensity in the nearest street, and traffic intensity in a 100 m buffer. Associations with IMT and ABI were estimated using linear regression and multinomial logistic regression, respectively, controlling for sex, age, smoking status, education, marital status, and several other potential confounders or intermediates. Results: Exposure contrasts between the 5th and 95th percentiles for NO2 (25 μg/m), traffic intensity in the nearest street (15,000 vehicles/day), and traffic load within 100 m (7,200,000 vehicle-m/day) were associated with differences of 0.56% (95% CI: –1.5, 2.6%), 2.32% (95% CI: 0.48, 4.17%), and 1.91% (95% CI: –0.24, 4.06) percent difference in IMT, respectively. Exposures were positively associated with an ABI of > 1.3, but not an ABI of < 0.9. Stronger associations were observed among those with a high level of education and in men ≥ 60 years of age. Conclusions: Long-term traffic-related exposures were associated with subclinical markers of atherosclerosis. Prospective studies are needed to confirm associations and further examine differences among population subgroups.key words: ankle–brachial index, average daily traffic, cardiovascular disease, exposure assessment, exposure to tailpipe emissions, intima media thickness, land use regression model, Mediterranean diet, nitrogen dioxide

A multi-screening approach for marine-derived fungal metabolites and the isolation of cyclodepsipeptides from Beauveria felina

Extracts obtained from 57 marine-derived fungal strains were analyzed by HPLC-PDA, TLC and ¹H NMR. The analyses showed that the growth conditions affected the chemical profile of crude extracts. Furthermore, the majority of fungal strains which produced either bioactive of chemically distinctive crude extracts have been isolated from sediments or marine algae. The chemical investigation of the antimycobacterial and cytotoxic crude extract obtained from two strains of the fungus Beauveria felina have yielded cyclodepsipeptides related to destruxins. The present approach constitutes a valuable tool for the selection of fungal strains that produce chemically interesting or biologically active secondary metabolites.

Validation of an analytical methodology for the quantitative analysis of petroleum hydrocarbons in marine sediment samples

This work describes a validation of an analytical procedure for the analysis of petroleum hydrocarbons in marine sediment samples. The proposed protocol is able to measure n-alkanes and polycyclic aromatic hydrocarbons (PAH) in samples at concentrations as low as 30 ng/g, with a precision better than 15% for most of analytes. The extraction efficiency of fortified sediments varied from 65.1 to 105.6% and 59.7 to 97.8%, for n-alkanes and PAH in the ranges: C16 - C32 and fluoranthene - benzo(a)pyrene, respectively. The analytical protocol was applied to determine petroleum hydrocarbons in sediments collected from a marine coastal zone.