Damages caused by hurricane Irma in the human-degraded mangroves of Saint Martin (Caribbean).

In early September 2017, Irma was the most powerful hurricane that struck the northern Caribbean over the last 100 years. In the 21st century, the stronger types of tropical cyclones will likely increase in frequency due to the climate change and internal climate variability. Lessons to anticipate the response of mangroves to this intensification can be learned from this extreme event. Here, we analysed damages caused in mangrove forests of the Saint Martin Island. Mangroves of this island were previously degraded due to historic human pressures and recent over-urbanisation. Forest inventories and time series of very high resolution satellite images revealed that approximately 80% of the mangrove area was damaged by the hurricane. Results highlighted distinct rates of forest recovery. Early and rapid recoveries were largely observed in most study sites. However, some mangroves were still unable to recover fourteen months after the disturbance. The human-induced degradation of the ecosystem prior to the hurricane is hypothesised to be the main factor controlling the absence of forest recovery. We suggest that human-degraded mangroves will be weakened in the face of such extreme events. We advocate to preserve and restore mangroves in order to guarantee all the valuable ecosystem services they provided.

Limited impact of several years of pretreated wastewater discharge on fauna and vegetation in a mangrove ecosystem.

It was hypothesized that mangroves, tropical wetlands, could be used for the finishing treatment of domestic wastewaters. Our aim was to determine if a nutrient-stressed mangrove could tolerate long-term discharges of pretreated wastewater (PW). Since 2008, in an in situ experimental system set up in Mayotte Island (Indian Ocean), domestic PW are discharged into two impacted areas (675 m2) dominated by different species of mangrove trees. Anthropogenic inputs during > 4.5 years led to an increase in vegetation growth associated with an increase in leaf pigment content, leaf surface and tree productivity. A marked increase in tree mortality was observed. There was no effect on crabs and meiofauna densities, but significant modifications of community structures. These effects may be directly linked to PW inputs, or indirectly to the modifications of the environment associated with higher tree growth. However, our results indicate that there was no major dysfunction the ecosystem.

Water circulation and governing factors in humid tropical river basins in the central Western Ghats, Karnataka, India.

RATIONALE: The small river basins in the narrow stretch of the Arabian Sea coast of southwest India experience high annual rainfall (800-8000 mm), with a higher proportion (85 %) during the summer monsoon period between June and September. This is due to a unique orographic barrier provided by the Western Ghats mountain belt (600-2600 m) for the summer monsoon brought by the southwesterly winds. This study is the first of a kind focusing on the water cycle with an intensive stable isotopes approach (samples of river water, groundwater, rainwater; seasonal and spatial sampling) in this part of the Western Ghats in Karnataka and also in the highest rainfall-receiving region (with places like Agumbe receiving 7000-8000 mm annual rainfall) in South India. In addition, the region lacks sustainable water budgeting due to high demographic pressure and a dry pre-monsoon season as the monsoon is mainly unimodal in this part of India, particularly close to the coast. METHODS: The stable isotopic compositions of groundwater, river water and rainwater in two tropical river basins situated approximately 60 km apart, namely the Swarna near Udupi and the Nethravati near Mangalore, were studied from 2010 to 2013. The δ(18)O and δ(2)H values of the water samples were measured by isotope ratio mass spectrometry, and the d-excess values calculated to better understand the dominant source of the water and the influence of evaporation/recycling processes. RESULTS: The water in the smaller area basin (Swarna basin) does not show seasonal variability in the δ(18)O values for groundwater and river water, having a similar mean value of -3.1 ‰. The d-excess value remains higher in both wet and dry seasons suggesting strong water vapor recycling along the foothills of the Western Ghats. In contrast, the larger tropical basin (Nethravati basin) displays specific seasonal isotopic variability. The observation of higher d-excess values in winter with lower δ(18)O values suggests an influence of northeast winter monsoon water in the larger basin. CONCLUSIONS: The narrow coastal strip to the west of the Western Ghats displays unique water characteristics in both tropical river basins investigated. For the smaller and hilly Swarna basin, the dense vegetation (wet canopies) could largely re-evaporate the (intercepted) rain, leading to no marked seasonal or altitude effect on the water isotope values within the basin. The larger Nethravati basin, which stretches farther into the foothills of the Western Ghats, receives winter monsoon water, and thus exhibits a clear seasonal variability in rainfall moisture sources. The degree of water vapor recycling in these wet tropical basins dominates the isotopic composition in this narrow coastal stretch of South India. An insight into the soil water contribution to the river water and groundwater, even in the rainfall-dependent tropical basins of South India, is provided in this study.

First assessment of water and carbon cycles in two tropical coastal rivers of south-west India: an isotopic approach.

RATIONALE: The contribution of tropical coastal rivers to the global carbon budget remains unmeasured, despite their high water dynamics, i.e. higher run-off with their basin characteristic of warm temperature. Two rivers draining the western part of the Western Ghats, the Swarna (length 80 km) and Nethravati (147 km) Rivers, were studied for water and carbon cycles. METHODS: The stable isotope ratios of oxygen (δ(18) O values), hydrogen (δ(2) H values) and carbon (δ(13) C values) were used to understand the water circulation, the weathering processes and the carbon biogeochemical cycle. The river water samples were collected during the dry post-monsoonal season (November 2011). RESULTS: The δ(18) O and δ(2) H values of river water suggested that the monsoonal vapour source and its high recycling have a dominant role because of the orographical and tropical conditions. The absence of calcareous rocks has led to dissolved inorganic carbon (DIC) mainly originating from atmospheric/soil CO2 , via rock-weathering processes, and the low soil organic matter combined with high run-off intensity has led to low riverine dissolved organic carbon (DOC) contents. The δ(13) C values increase from upstream to downstream and decrease with increasing pCO2 . There is a positive relationship between the δ(13) CDIC values and the DOC concentrations in these two rivers that is contrary to that in most of the studied rivers of the world. CONCLUSIONS: The higher evapotranspiration supported by tropical conditions suggests that there are higher vapour recycling process in the Swarna and Nethravati basins as studied from the water δ(18) O and δ(2) H values. The basin characteristics of higher rainfall/run-off accompanied by warm temperature suggest that the δ(13) C value of riverine DIC is mainly controlled by the weathering of source rocks (silicates) with variation along the river course by CO2 degassing from the river water to the atmosphere and is less dominated by the oxidation of DOC.

Isotopic values of the Amazon headwaters in Peru: comparison of the wet upper Río Madre de Dios watershed with the dry Urubamba-Apurimac river system.

RATIONALE: The Amazon River is a huge network of long tributaries, and little is known about the headwaters. Here we present a study of one wet tropical Amazon forest side, and one dry and cold Atiplano plateau, originating from the same cordillera. The aim is to see how this difference affects the water characteristics. METHODS: Different kind of water (spring, lake, river, rainfall) were sampled to determine their stable isotopes ratios (oxygen 18/16 and hydrogen 2/1) by continuous flow isotope ratio mass spectrometry (IRMS). These ratios coupled with chemical analysis enabled us to determine the origin of the water, the evaporation process and the water recycling over the Amazon plain forest and montane cloud forest. RESULTS: Our study shows that the water flowing in the upper Madre de Dios basin comes mainly from the foothill humid forest, with a characteristic water recycling process signature, and not from higher glacier melt. On the contrary, the water flowing in the Altiplano Rivers is mainly from glacier melts, with a high evaporation process. This snow and glacier are fed mainly by Atlantic moisture which transits over the large Amazon forest. CONCLUSIONS: The Atlantic moisture and its recycling over this huge tropical forest display a progressive isotopic gradient, as a function of distance from the ocean. At the level of the montane cloud forest and on the altiplano, respectively, additional water recycling and evaporation occur, but they are insignificant in the total water discharge.

Tracing the sources of water using stable isotopes: first results along the Mangalore-Udupi region, south-west coast of India.

The Mangalore and Udupi region on the south-west coast of India is characterized by small west-flowing rivers (150-250 km in length) originating in the Western Ghats (up to 1940 meters above sea level (m asl)) and joining the Arabian Sea. The area experiences a humid tropical climate with frequent, high-intensity rainfall (4000 mm annual average). Nevertheless, there is a shortage of water during the peak dry season immediately before the onset of monsoon because of a rapid fall in the groundwater level. From the humid high-altitude forests to the intense agriculture in the coastal area, there is an urgent need to understand the movement of water between evapotranspiration, rainfall, river systems and the groundwater compartments in order to achieve better water resource management. Demographic pressure on the area with over half a million inhabitants and industrial activity strongly influence this fragile ecosystem. The coastal area is characterized by shallow open wells, which are particularly sensitive to pollution and eutrophication. Stable water isotopes ((18)O and deuterium) were used for the first time in this region to determine the isotopic characteristics of the different waters. There is a clear seasonal difference in the isotopic ratios and d-excess values between the summer and winter monsoon periods, with a predominance of lighter isotopes in the latter period. No significant variations in isotopic ratios were observed in relation to altitude because of the possible role of mist formation at high altitude. Greater d-excess values were observed in the west-flowing streams than in rivers flowing east on account of the moist westerly oceanic winds and water vapour recycling.

The use of stable isotopes to evaluate water mixing and water use by flood plain trees along the Garonne valley.

Before the confluence of the Tarn, the Garonne valley was the driest area in the entire south-west of France, due to the relatively low rainfall and low summer discharge of the Garonne River and its tributaries. The natural abundance of the stable isotope of oxygen (18O) and ionic charge of surface and ground water were used to estimate the water source for the Garonne River and phreatic subsurface water. We also measured these constituents in the sap of trees at several flood plain sites to better understand the source of water used by these trees. 18O signatures and conductivity in the Garonne River indicated that the predominance of water was from high altitude surface runoff from the Pyrenees Mountains. Tributary inputs had little effect on isotopic identity, but had a small effect on the conductivity. The isotopic signature and ionic conductivity of river water (delta18O: -9.1 per thousand to -9.0 per thousand, conductivity: 217-410 microS/cm) was distinctly different from groundwater (delta18O: -7.1 per thousand to -6.6 per thousand, conductivity: 600-900 microS/cm). Isotopic signatures from the sap of trees on the flood plain showed that the water source was shallow subsurface water (<30 cm), whereas trees further from the river relied on deeper ground water (>1 m). Trees at both locations maintained sap with ionic charges much greater (2.3-3.7x) than that of source water. The combined use of 18O signatures and ionic conductivity appears to be a potent tool to determine water sources on geographic scales, and source and use patterns by trees at the local forest scale. These analyses also show promise for better understanding of the effects of anthropogenic land-use and water-use changes on flood plain forest dynamics.

Copper-ligand interactions and physiological free radical processes. Part 2. Influence of Cu2+ ions on Cu(+)-driven .OH generation and comparison with their effects on Fe(2+)-driven .OH production.

In our search to establish a reference .OH production system with respect to which the reactivity of copper(II) complexes could then be tested, the influence of free Cu2+ ions on the Cu+/H2O2 reaction has been investigated. This influence depends on the CCu2+/CCu+ ratio. At low Cu2+ concentrations, .OH damage to various detector molecules decreases with increasing Cu2+ concentrations until CCu2+/CCu+ reaches unity. Above this value, .OH damage increases sharply until CCu2+/CCu+ becomes equal to 5 with salicylate and 2 with deoxyribose, ratios for which the protective effect of Cu2+ cancels. Finally, at higher concentrations, Cu2+ ions logically add their own .OH production to that normally expected from Cu+ ions. The possible origin of this unprecedented alternate effect has been discussed. The possible influence of Cu+ ions on the generation of .OH radicals by water gamma radiolysis has also been tested and, as already established for Cu2+ in a previous work, shown to be nonexistent. This definitely confirms that either form of ionised copper cannot scavenge .OH radicals in the absence of a ligand.

A quantitative investigation of proton- and lead(II)-dithioerythritol complex equilibria under physiological conditions.

Dithioerythritol (DTE) is frequently employed as a reducing agent or a protective reagent for thiol groups in biological assays. Owing to its known inhibiting properties in enzyme catalysis reactions, lead is also commonly used in such experiments, and often simultaneously with DTE. Given the potential affinity of these two reactants, their measured individual effects may well depend on their interactions in the medium used. Any quantitative assessment of these interactions necessitates, however, that the complex equilibria between lead and DTE be investigated beforehand. To test this hypothesis, the formation constants of lead(II) complexes with DTE under physiological conditions (37 degrees, NaCl 0.15M) have been calculated from the results of glass electrode potentiometry, with the help of the MINIQUAD and ESTA computer programs. The pK values for dissociation of DTE have been found equal to 8.926 +/- 0.003 and 9.840 +/- 0.003. The following lead-DTE species have been characterized: ML (12.774 +/- 0.037), MLH(-1) (2.858 +/- 0.037), M(2)LH(-1) (13.349 +/- 0.025) and M(6)L(5) (86.586 +/- 0.099); the log *beta-values are given in the parentheses. Appropriate computer simulations effectively show that the interactions of the two reactants are indeed quite significant within the concentration ranges commonly used in in vitro biological assays. They should thus be taken into account in interpretation of the effects observed.

Copper-ligand interactions and physiological free radical processes. pH-dependent influence of Cu2+ ions on Fe2(+)-driven OH. generation.

Prior to comparative studies on the reactivity of various copper complexes with respect to OH. radicals, the influence of free Cu2+ ions on the superoxide-independent generation of OH. radicals through Fenton assays and water gamma radiolysis has been tested in the present work. Cu2+ ions have been shown to behave in a distinct manner towards each of these two production systems. As was logically expected from the noninvolvement of copper in OH. radical production through gamma radiolysis, no influence of Cu2+ ions has been observed on the amount of radicals detected in that case. In contrast, Cu2+ ions do influence OH. radical generation through iron-driven Fenton reactions, but differently depending on copper concentration. When present in high concentrations, Cu2+ ions significantly contribute to OH. radical production, which confirms previous observations on the reactivity of these in the presence of hydrogen peroxide. At lower levels corresponding to copper/iron ratios below unity on the contrary, Cu2+ ions behave as inhibitors of the OH. production in a pH-dependent manner over the 1-6 range investigated: the lower the pH, the greater the inhibition. The possible origin of this previously unreported inhibitory effect is discussed.

Metal ion-tetracycline interactions in biological fluids. Part 8. Potentiometric and spectroscopic studies on the formation of Ca(II) and Mg(II) complexes with 4-dedimethylamino-tetracycline and 6-desoxy-6-demethyl-tetracycline.

Effects of metal ion-tetracycline (TC) interactions on both gastrointestinal absorption and pharmacological activity of these drugs are well documented. In particular, recent simulation studies based on newly determined complex stability constants have drawn attention to the potential influence of Ca2+ and Mg2+ ions on the bioavailability of various TC derivatives in blood plasma. Contrary to previous thoughts, it was demonstrated in these studies that the fraction of antibiotic not bound to proteins almost exclusively occurs as calcium and magnesium complexes. Among this fraction, predominant binuclear species are electrically charged, and as such cannot passively diffuse through cell membranes. It was thus postulated that the partial blocking of one of the potential coordination sites of the TC molecule, which would favor the formation of neutral mononuclear complexes, should result in a better tissue penetration of the drug. Such correlations were recently established for specific derivatives. Before possible modifications of the TC molecule can be envisaged, it is necessary that all the chelating sites involved in the relevant complexes be properly assigned. As tetracyclines are very complex ligands, the present paper first deals with the coordination of calcium and magnesium with two simpler parent substances, i.e., 4-dedimethylamino-tetracycline (DTC) and 6-desoxy-6-demethyl-tetracycline (DSC). After the quantitative investigation of the proton and metal complex equilibria involved, UV and circular dichroism spectroscopies are used to study the corresponding structural aspects. In DTC complexes, the BCD ring system acts as the exclusive coordination site for both metals. For DSC, however, the N4 atom plays a leading role in the metal binding and would be the only donor involved in 1:1 species; in ML2 complexes, the second ligand is thought to bind through the BCD ring system.

Metal ion-tetracycline interactions in biological fluids. Part 5. Formation of zinc complexes with tetracycline and some of its derivatives and assessment of their biological significance.

A series of studies was previously devoted to the dependence of the bioavailability of various tetracyclines on their coordination with calcium and magnesium ions. Several clinical investigations have also shown zinc to interfere with the gastrointestinal absorption of the drug in humans. On the other hand, the administration of tetracycline to rats was reported to result in the increase of the elimination rate of zinc, which could originate in zinc-tetracycline interactions in blood plasma. Formation constants for zinc complexes with tetracycline, oxytetracycline, doxycycline, minocycline, chlortetracycline and demethylchlortetracycline were thus determined at 37 degrees C in NaCl 0.15 mol. dm-3 aqueous medium. Computer simulations were then carried out to investigate the drug influence on the distribution of the low-molecular-weight fraction of zinc in human blood plasma. Zinc-tetracycline interactions in the gastrointestinal fluid were also simulated, using clinical data relative to fasting subjects as taken from the literature. No significant effect can be expected from tetracyclines on the distribution of zinc in plasma at the usual therapeutic levels. However, zinc-tetracycline interactions have been found to be determining factors for the bioavailabilities of the metal as well as of the antibiotic in the gastrointestinal fluid.

Metal ion-tetracycline interactions in biological fluids. Part 3. Formation of mixed-metal ternary complexes of tetracycline, oxytetracycline, doxycycline and minocycline with calcium and magnesium, and their involvement in the bioavailability of these antibiotics in blood plasma.

The equilibria of the complexes formed separately by calcium and magnesium with tetracycline, oxytetracycline, doxycycline and minocycline were studied in the previous parts of this series. Computer simulations run on this occasion showed that the stoichiometry of these species do actually condition the bioavailability of the antibiotics in blood plasma during treatment, the fraction of free base being quite negligible with regard to the metal-bound one. The present paper completes this study with the investigation of the mixed-metal complexes given rise to by calcium and magnesium with the same antibiotics. Such ternary species have been proved to exist for tetracycline, oxytetracycline, and minocycline. Their involvement in the plasma distribution of these drugs is discussed, in relation with the potential abilities of the four tetracyclines to diffuse from plasma into tissue membranes.

Metal ion-tetracycline interactions in biological fluids. 2. Potentiometric study of magnesium complexes with tetracycline, oxytetracycline, doxycycline, and minocycline, and discussion of their possible influence on the bioavailability of these antibiotics in blood plasma.

The formation constants of the various complexes formed by magnesium with four tetracycline derivatives, namely, tetracycline itself, oxytetracycline, doxycycline, and minocycline, were determined by potentiometry over large pH ranges under experimental conditions pertaining to blood plasma (37 degrees C, NaCl 0.15 mol dm-3). The results were used, together with those previously obtained on the complexation of these tetracyclines with proton and calcium, to assess the influence of the two alkali earth metal ions on the bioavailability of these drugs in blood plasma. Accordingly, simulations of the distribution of the four tetracyclines into their different proton and metal complex species were calculated. The distributions confirm that, in combination with the protein-bound fraction of the tetracyclines, the metal-bound fraction represents more than 99% of these drugs in plasma, the extent of their free fraction commonly being less than 1%.