The chemical changes of DOM from black waters to coastal marine waters by HPLC combined with ultrahigh resolution mass spectrometry

How dissolved organic matter (DOM) undergoes chemical changes during its transit from river to ocean remains a challenge due to its complex structure. In this study, DOM along a river transect from black waters to marine waters is characterized using an offline combination of reversed-phase high performance liquid chromatography (RP-HPLC) coupled to electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS), as well as tandem ESI-FTICR-MS. In addition, a water extract from degraded wood that mainly consists of lignins is used for comparison to the DOM from this transect. The HPLC chromatograms of all DOM samples and the wood extract show two major well-separated components; one is hydrophilic and the other is hydrophobic, based on their elution order from the C₁₈ column. From the FTICR-MS analysis of the HPLC fractions, the hydrophilic components mainly contain low molecular weight compounds (less than 400 Da), while the hydrophobic fractions contain the vast majority of compounds of the bulk C₁₈ extracted DOM. The wood extract and the DOM samples from the transect of black waters to coastal marine waters show strikingly similar HPLC chromatograms, and the FTICR-MS analysis further indicates that a large fraction of molecular formulas from these samples are the same, existing as lignin-like compounds. Tandem mass spectrometry experiments show that several representative molecules from the lignin-like compounds have similar functional group losses and fragmentation patterns, consistent with modified lignin structural entities in the wood extract and these DOM samples. Taken together, these data suggest that lignin-derived compounds may survive the transit from the river to the coastal ocean and can accumulate there because of their refractory nature.     

Chemical structural models for coalified wood (vitrinite) in low rank coal

Examination of a series of coalified gymnospermous woods ranging in rank from brown coal to subbituminous coal by solid-state ¹³C NMR and analytical pyrolysis has provided sufficient information to construct structural models depicting the changes that occur to lignin, the primary precursor of vitrinite, during coalification. Progressive changes in the chemistry of coalified wood suggest the following series of reactions: (1) demethylation to form catechol-like structures that are dominant components of brown coal and lignite A; (2) cleavage of aryl ether linkages to form phenols and reactive carbocations that alkylate the catechol rings; (3) dehydration of the catechol rings; (3) dehydration of the catechol-like structures to form the structures of subbituminous coal dominated by alkylphenols; and (4) reduction of the 3-carbon alkyl side chain derived from lignin to form propyl substituents. The models developed for each stage of coalification are derived from chemical modifications of the structure of lignin.     

Cape cormorants decrease,move east and adapt foraging strategies following eastward displacement of their main prey

Numbers of Cape cormorants Phalacrocorax capensis breeding in South Africa decreased by nearly 50% from approximately 107 000 pairs in 1977–1981 to 57 000 pairs in 2010–2014. Although four colonies had >10 000 pairs in 1977–1981, there was just one such colony in 2010–2014. Almost all the decrease occurred after the early 1990s off north-west South Africa, between the Orange River estuary and Dassen Island. South of this, the number breeding in the two periods was stable, with some colonies being formed or growing rapidly in the 2000s. The proportion of South Africa’s Cape cormorants that bred south of Dassen Island increased from 35% in 1977–1981 to 66% in 2010–2014, with the opposite situation observed in the north-west. This matched a shift to the south and east in the distributions of two of the Cape cormorant’s main prey species, anchovy Engraulis encrasicolus and sardine Sardinops sagax. In 2014, an apparent scarcity of prey in the north-west resulted in Cape cormorants attempting to take bait from hooks of fishing lines over an extended period, a behaviour not previously recorded. The number of Cape cormorants breeding in the south may be constrained by the absence of large islands between Dyer Island in the west and Algoa Bay in the east. If so, it may be possible to bolster the southern population through the provision of appropriate breeding habitat, such as platforms, or restricting human disturbance at suitable mainland cliff breeding sites.     

1H and 13C NMR of marine humic acids

¹³C and ¹H NMR spectra were obtained for humic acids isolated from marine sediments. NMR shows great promise in identifying structural components of humic acids as some new and interesting structural features are identified. Aliphatic structures were found to constitute a much larger fraction of humic acids than previously thought, and they appeared to be highly branched. Although the aromatic content of terrestrial humic acid was found to be lower than expected, the aromaticity appears to be a specific discriminator of terrestrial/aquatic source types. A humic acid isolated from an anoxic algal sapropel was found to be composed predominantly of polyuronic acids and different than other aquatic sedimentary humic substances.     

Polychlorinated biphenyls in sewage sludge and sediments of the New York Bight

Sediments of the New York Bight were analysed for polychlorinated biphenyls (PCB) and found to be heavily contaminated by such substances. The highest concentrations are adjacent to an offshore sludge dump zone, implying that the primary source of PCBs is sewage sludge in the area under consideration. Widespread transport of PCBs out of the bight is not evident as the area of contamination is limited to areas of mud accumulation. The PCB profile in a core of these mud facies can be historically correlated to the commercial production of PCBs.     

Temporal variability in sources of dissolved organic carbon in the lower Mississippi river

Here we report on the temporal changes in the composition of dissolved organic carbon (DOC) collected in the tidal freshwater region of the lower Mississippi River. Lignin-phenols, bulk stable carbon isotopes, compound-specific isotope analyses (CSIA) and ¹³C nuclear magnetic resonance (NMR) spectrometry were used to examine the composition of high molecular weight dissolved organic matter (HMW DOM) at one station in the lower river over 6 different flow regimes in 1998 and 1999. It was estimated that the annual input of DOC delivered to the Gulf of Mexico from the Mississippi River was of 3.1 × 10⁻³ Pg, which represents 1.2% of the total global input of DOC from rivers to the ocean. Average DOC and HMW DOC were 489 ±163 and 115 ± 47 μM, respectively. ¹³C-NMR spectra revealed considerably more aliphatic structures than aromatic carbons in HMW DOC. Lignin phenols were significantly ¹³C-depleted with respect to bulk HMW DOM indicating that C₄ grass inputs to the HMW DOM were not significant. It is speculated that C₄ organic matter in the river is not being converted (via microbial decay) to HMW DOM as readily as C₃ organic matter is, because of the association of C₄ organic matter with finer sediments. The predominantly aliphatic ¹³C NMR signature of HMW DOM suggests that autochthonous production in the river may be more important as a source of DOC than previously thought. Increases in nutrient loading and decreases in the suspended load (because of dams) in the Mississippi River, as well as other large rivers around the world, has resulted in significant changes in the sources and overall cycling of riverine DOC.     

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.     

Numerical study of circulation and temperature-salinity distributions in the Bras d’Or Lakes

The Bras d’Or Lakes (BdOL) are a large, complex and virtually land-locked estuary in central Cape Breton Island of Nova Scotia and one of Canada’s charismatic ecosystems, sustaining ecological and cultural communities unique in many aspects. The BdOL comprise two major basins, many deep and shallow bays, several narrow channels and straits and a large, geologically complex watershed. Predictive knowledge of the water movement within the estuary is a key requirement for effective management and sustainable development of the BdOL ecosystem. A three-dimensional (3D) primitive-equation ocean circulation model is used to examine the estuary’s response to tides, winds and buoyancy forcing associated with freshwater runoff in a series of numerical experiments validated with empirical data. The model results generate intense, jet-like tidal flows of about 1 m s^?1 in the channels between the basins and connecting them to the ocean and relatively weak tidal currents in other regions, which agrees well with previous observations and numerical results. Wind forcing and buoyancy forcing associated with river runoff play important roles in generating the significant sub-tidal circulations in the estuary, including narrow channels, deep basins and shallow bays. The circulation model is also used to reconstruct the 3D circulation and temperature-salinity distributions in the summer months of 1974, when current and hydrographic measurements were made at several locations. The sub-tidal circulation in the estuary produced by the model is characterised by wind and barometric set-up and set-down in different sections of the system, and a classic two-layer estuarine circulation in which brackish, near-surface waters flow seaward from the estuary into the Atlantic Ocean, and deep salty waters flow landward through the major channel. The model results reproduce reasonably well the overall features of observed circulation and temperature-salinity fields made in the BdOL in 1974 but generally underestimate the observed currents and density stratification. The model discrepancies reflect the use of spatially mean wind forcing and spatially and monthly mean surface heat flux and the inability of the coarse model horizontal resolution (～500 m) to resolve narrow channels and straits.     

Patterns and trends in seabird bycatch in the pelagic longline fishery off South Africa

Both foreign and domestic pelagic longline fishing vessels operate in South Africa’s Exclusive Economic Zone and adjacent international waters where they kill hundreds of seabirds each year as bycatch. To update assessments of the impact of the pelagic longline fishery on seabirds off South Africa, information on necropsied seabirds and national fisheries observer bycatch records were summarised for 2006–2013. Foreign-flagged (Asian) vessels had 100% observer coverage throughout the study period, whereas only 6% of the fishing effort by South African-flagged vessels was observed (with no coverage in 2011–2013). Vessels with observers caught seabirds at a rate of 0.132 birds per 1 000 hooks, resulting in an estimated mortality of 2 851 individuals (356 per year) comprising 14 species. Extrapolation of the observed fishing sets to the unobserved fishing sets by the South African domestic longline fleet suggested that approximately 750 additional birds were likely killed during the study period, therefore a combined 450 birds were killed per year. White-chinned petrel Procellaria aequinoctialis was the most frequently killed species (66%), followed by ‘shy-type’ albatrosses Thalassarche cauta/steadi (21%), black-browed albatross T. melanophris (7%), Indian yellow-nosed albatross T. carteri (3%), and Cape gannet Morus capensis (2%). The seabird bycatch rates were lower than in 1998–2005. Nationality of the vessel, time of line-setting, moon phase, year, season, fishing area, and seabird bycatch mitigation measures all influenced seabird mortality. Concurrent with 100% observer coverage, significant reductions in the seabird bycatch rate occurred in the Asian fleet in the latter years of the study, and these rates now approximate the national target (0.05 birds per 1 000 hooks). However, seabird bycatch rates remained high in the South African fleet, where no observers were deployed during 2011–2013, highlighting the need for independent observer programmes in fisheries—a matter of global interest. Suggestions are made as to how seabird bycatch by pelagic longline fisheries off South Africa may be further reduced.     

Early maturation processes in coal. Part 1: Pyrolysis mass balance and structural evolution of coalified wood from the Morwell Brown Coal seam

We have developed a theoretical approach for evaluating the maturation of kerogen-like material, involving molecular dynamic reactive modelling with a reactive force field to simulate thermal stress. Morwell Brown Coal was selected to study the thermal evolution of terrestrial organic matter (OM). To achieve this, a structural model is first constructed on the basis of literature models and analytical characterization of our samples using modern 1and 2D nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy and elemental analysis. Then, artificial maturation of the coal is performed at low conversion in order to obtain quantitative and qualitative detailed evidence for the structural evolution of the kerogen upon maturation. The chemical changes include defunctionalization of carboxyl, carbonyl and methoxy functional groups, coupled with an increase in cross linking in the residual matured kerogen. Gaseous and liquid hydrocarbons, essentially CH₄, C₄H₈ and C₁₄₊ hydrocarbons, are generated in low amount, merely via cleavage of the lignin side chain.