A new typology of benefits derived from marine protected areas

Global decline of marine resources has triggered a worldwide demand for changing the way ocean resources are managed. Ecosystem-based management approaches have emerged using marine protected areas (MPA) as the main tool. Several classifications of marine protected areas benefits have been made, but all have focused only on the benefits to humans, neglecting many important benefits accrued to nature. This paper presents a new comprehensive classification of MPA benefits that will provide scientists and managers with an inclusive framework to accurately identify and account for all possible benefits derived from MPAs. The paper also analyses the methods available for valuing these benefits. A total of 99 benefits were identified within nine main categories: fishery, non-fishery, management, education/research, cultural, process, ecosystem, population and species benefits. These categories are arranged in two main divisions (direct and indirect benefits), which, at the same time, fall within the realms of benefits to humans and to nature.     

13C Nuclear magnetic resonance studies of kerogen from Cretaceous black shales thermally altered by basaltic intrusions and laboratory simulations

Cretaceous black shales from DSDP Leg 41, Site 368 in the Eastern Atlantic Ocean were thermally altered during the Miocene by an intrusive basalt. The sediments overlying and underlying the intrusive body were subjected to high temperatures (up to ~ 500°C) and, as a result, their kerogen was significantly altered. The extent of this alteration has been determined by examination by means of ¹³C nuclear magnetic resonance, using cross polarization/magic-angle spinning (CP/MAS). Results indicate that the kerogen becomes progressively more aromatic in the vicinity of the intrusive body. Laboratory heating experiments, simulating the thermal effects of the basaltic intrusion, produced similar results on unaltered shale from the drill core. The ¹³C CP/MAS results appear to provide a good measure of thermal alteration.     

Use of solid-state 13C NMR in structural studies of humic acids and humin from Holocene sediments

¹³C NMR spectra of solid humic substances in Holocene sediments have been obtained using cross polarization with magic-angle sample spinning techniques. The results demonstrate that this technique holds great promise for structural characterizations of complex macromolecular substances such as humin and humic acids. Quantifiable distinctions can be made between structural features of aquatic and terrestrial humic substances. The aliphatic carbons of the humic substances are dominant components suggestive of input from lipid-like materials. An interesting resemblance is also noted between terrestrial humic acid and humin spectra.     

Tectonic reconstruction of the northern Andean blocks: Oblique convergence and rotations derived from the kinematics of the Piedras–Girardot area, Colombia

A detailed kinematic study in the Piedras–Girardot area reveals that approximately 32 km of ENE–WSW oblique convergence is accommodated within a northeast-trending transpressional shear zone with a shear strain of 0.8 and a convergence factor of 2. Early Campanian deformation is marked by the incipient propagation of northeast-trending faults that uplifted gentle domes where the accumulation of sandy units did not take place. Maastrichtian unroofing of a metamorphic terrane to the west is documented by a conglomerate that was deformed shortly after deposition developing a conspicuous intragranular fabric of microscopic veins that accommodates less than 5% extension. This extensional fabric, distortion of fossil molds, and a moderate cleavage accommodating less than 5% contraction, developed concurrently, but before large-scale faulting and folding. Paleogene folding and southwestward thrust sheet propagation are recorded by syntectonic strata. Neogene deformation took place only in the western flank of this foldbelt. The amount, direction, and timing of deformation documented here contradict current tectonic models for the Cordillera Oriental and demand a new tectonic framework to approach the study of the structure of the northern Andes. Thus, an alternative model was constructed by defining three continental blocks: the Maracaibo, Cordillera Central, and Cordillera Oriental blocks. Oblique deformation imposed by the relative eastward and northeastward motion of the Caribbean Plate was modeled as rigid-body rotation and translation for rigid blocks (derived from published paleomagnetic and kinematic data), and as internal distortion and dilation for weak blocks (derived from the Piedras–Girardot area). This model explains not only coeval dextral and sinistral transpression and transtension, but also large clockwise rotation documented by paleomagnetic studies in the Caribbean–northern Andean region.     

Degradation of carbohydrates and lignins in buried woods

Spruce, alder, and oak woods deposited in coastal sediments were characterized versus their modern counterparts by quantification of individual neutral sugars and lignin-derived phenols as well as by scanning electron microscopy, ¹³C NMR, and elemental analysis. The buried spruce wood from a 2500 yr old deposit was unaltered whereas an alder wood from the same horizon and an oak wood from an open ocean sediment were profoundly degraded. Individual sugar and lignin phenol analyses indicate that at least 90 and 98 wt% of the initial total polysaccharides in the buried alder and oak woods, respectively, have been degraded along with 15–25 wt% of the lignin. At least 75% of the degraded biopolymer has been physically lost from these samples. This evidence is supported by the SEM, ¹³C NMR and elemental analyses, all of which indicate selective loss of the carbohydrate moiety. The following order of stability was observed for the major biochemical constituents of both buried hardwoods: vanillyl and $\text{p-}\text{hydroxyl}$ lignin structural units > syringyl lignin structural units > pectin > α-cellulose > hemicellulose. This sequence can be explained by selective preservation of the compound middle lamella regions of the wood cell walls. The magnitude and selectivity of the indicated diagenetic reactions are sufficient to cause major changes in the chemical compositions of wood-rich sedimentary organic mixtures and to provide a potentially large in situ nutrient source.     

Carbon isotope fractionation of sapropelic organic matter during early diagenesis

Study of an algal, sapropelic sediment from Mangrove Lake, Bermuda shows that the mass balance of carbon and stable carbon isotopes in the major organic constituents is accounted for by a relatively straightforward model of selective preservation during diagenesis. The loss of ¹³C-enriched carbohydrates is the principal factor controlling the intermolecular mass balance of ¹³C in the sapropel. Results indicate that labile components are decomposed leaving as a residual concentrate in the sediment an insoluble humic substance that may be an original biochemical component of algae and associated bacteria. An overall decrease of up to about 4‰ in the δ ¹³C values of the organic matter is observed as a result of early diagenesis.     

Molecular characterization of dissolved organic matter (DOM) along a river to ocean transect of the lower Chesapeake Bay by ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) is utilized to molecularly characterize DOM as it is transported along a river to estuary to ocean transect of the lower Chesapeake Bay system. The ultrahigh resolving power (greater than 500,000) and mass accuracy of FTICR-MS allow for the resolution of the thousands of components in a single DOM sample, and can therefore elucidate the molecular-level changes that occur during DOM transformation from a terrestrial location to the marine environment. An important feature of FTICR-MS is that its sensitivity allows for direct analysis of low salinity samples without employing the traditional concentration approaches involving C₁₈ extraction or ultrafiltration. To evaluate the advantages of using direct analysis, a C₁₈ extract of riverine water is compared to its whole, unfractionated water, and it was determined that the C₁₈ extraction is selective in that it eliminates two major series of compounds. One group is aliphatic amines/amides that are not adsorbed to the C₁₈ disk because they exist as positive ions prior to extraction. The second group is tannin-like compounds with higher oxygen contents and a more polar quality that also allow them not to be adsorbed to the C₁₈ disk. This direct approach could not be used for brackish/saline waters, so the C₁₈ method is resorted to for those samples. Along the subject transect, a significant difference is observed in the molecular composition of DOM, as determined from assigned molecular formulas. The DOM tends to become more aliphatic and contain lower abundances of oxygen-rich molecules as one progresses from inshore to the offshore. A considerable amount of molecular formula overlap does exist between samples from sites along the transect. This can be explained as either the presence of refractory material that persists throughout the transect, due to its resistance to degradation, or that the assigned molecular formulas are the same but the chemical structures are different. ESI-FTICR-MS is a powerful technique for the investigation of DOM and has the ability to detect compositional variations along the river to ocean transect. Visualization tools such as two dimensional and three dimensional van Krevelen diagrams greatly assist in highlighting the shift from the more aromatic, terrestrial DOM to the more aliphatic, marine DOM.     

Does one size fit all? An evaluation of length–weight relationships for New Zealand's freshwater fish species

Length–weight relationships are a fundamental tool for assessing populations and communities in fisheries science. Many researchers have collected length–weight data throughout New Zealand, yet parameters describing these relationships remain unpublished for many species of freshwater fish. We compiled 285,124 fish records from researchers and institutions across New Zealand to parameterise length–weight equations, using both power and quadratic models, for 53 freshwater species belonging to 13 families. The influence of location and sex on length–weight relationships was also assessed. Location, in particular, generated different length–weight relationships for 65% of the species examined. Length–weight equations were validated by comparing predicted weights against independently measured weights from 25 electrofished sites across New Zealand and the equations were highly accurate (R²>0.99). Recommendations are made about how to robustly apply this new resource which should assist freshwater fisheries researchers throughout New Zealand.     

Early diagenesis of Botryococcus braunii race A as determined by high resolution magic angle spinning (HRMAS) NMR

An algal culture of Botryococcus braunii race A and its residue obtained after 201 days of oxic biodegradation are characterized using high resolution magic angle spinning (HRMAS) NMR spectroscopy, a hybrid technique which provides molecular details non-invasively. The high resolution of two dimensional NMR using HRMAS gives precise structural assignments of different classes of compounds contained in the initial algae and biodegraded algae. The data indicate that some intracellular lipids and proteinaceous materials are more environmentally labile while other long chain polymethylenic structures with ether functional groups, likely from algaenan, are observed to survive the degradation process. The identification of similar structural entities in both fresh and degraded material clearly points to selective preservation as the main process responsible for the early diagenetic transformation of this type of algae.     

Molecular characterization of Type I kerogen from the Green River Formation using advanced NMR techniques in combination with electrospray ionization/ultrahigh resolution mass spectrometry

This study describes a new approach for characterizing high molecular weight compounds in Type I kerogen, involving both nuclear magnetic resonance (NMR) spectroscopy and Fourier transform ion cyclotron mass spectrometry (FTICR-MS). Kerogen isolated from the Mahogany zone of the Green River Formation was examined directly using high resolution magic angle spinning (HRMAS) NMR to obtain liquid-like multidimensional spectra. It was then successively extracted with n-pentane, dichloromethane and pyridine. Pyridine extraction was also performed for comparison with the successive extractions. Using solid-state NMR, we show that the sum of the successive extracts and the single pyridine extract are quantitatively representative of the unextracted kerogen. This suggests that a non-invasive characterization of Green River kerogen can be obtained by examining the soluble extracts, all of which were subjected to ESI-FTICR-MS to identify a wide series of compounds. Series of polar CHO, CHOS and CHON compounds between C₁₂ and C₅₀₊ were found. In all the extracts the two homologous series of acids (C_nH_2nO₂ and C_nH_2n−2O₄) dominated. Collision-induced dissociation was also employed to identify the different functional groups comprising the different series. The CHO series contained carboxylic acid and alkoxyl groups, whereas the CHOS and CHON series contained sulfoxide groups and nitrile-type compounds. The results also show that pyridine extraction can be used either for screening a large series of samples or for the specific study of CHO compounds. However for a detailed and complete study of the different homologous series we recommend using the successive extraction protocol.