Carbon and nitrogen isotope evidence for widespread presence of anoxic intermediate waters before and during the Permian-Triassic mass extinction

The largest mass extinction since the advent of animals occurred during the Permian-Triassic (P-Tr) transition, ca. 252 Ma, and is commonly attributed to the eruption of the Siberian Traps large igneous province. However, the direct killing mechanism is still debated. In this study, we investigated marine redox conditions of the intermediate water column that most organisms inhabit with special attention to the time interval before the onset of the mass extinction. The carbon isotope composition of carbonate and organic carbon (δ13Ccarb and δ13Corg) as well as the nitrogen isotope composition of bulk nitrogen (δ15N) were analyzed in four P-Tr boundary sequences (Zhongli, Jianshi, Ganxi, and Chaotian sections), which record a transect from a shallow water carbonate platform to a deep water, lower ramp slope in South China. δ13Ccarb shows a distinct negative shift in all sections and displays a clear, 2−4‰, decreasing gradient accompanying an increase in water depth both before and after the mass extinction. A distinct negative shift in δ15N is observed in the shallow water Zhongli section, whereas a minor negative shift is present in the three deeper water sections. Before the mass extinction, the δ15N values from shallow water sections are higher than those from deeper waters. The low δ15N values close to 0‰ in deeper water sections suggest that microbial nitrogen fixation was the predominant source of biologically available nitrogen before the onset of the mass extinction. Thus, the water depth- dependent gradient in δ13Ccarb and δ15N suggests that an oxygen-deficient intermediate water column was already present before the mass extinction. The uniform δ15N values around 0‰ accompanying the onset of the mass extinction reveal that anoxic intermediate waters expanded into shallow waters. Meanwhile, the distinct positive shift in δ13Corg observed in upper ramp slope sections, i.e., the Jianshi and Ganxi sections, suggests that a euxinic photic zone was at least episodically present in the earliest Triassic. The temporal coincidence between the expansion of intermediate water column anoxia and the onset of the P-Tr mass extinction supports the hypothesis that marine anoxia was a direct killing mechanism.

Supplemental Material: Carbon and nitrogen isotope evidence for widespread presence of anoxic intermediate waters before and during the Permian-Triassic mass extinction

Table S1: Geochemical data.

Supplemental Material: Carbon and nitrogen isotope evidence for widespread presence of anoxic intermediate waters before and during the Permian-Triassic mass extinction

Table S1: Geochemical data.

Spatial patterns of ectoenzymatic kinetics in relation to biogeochemical properties in the Mediterranean Sea and the concentration of the fluorogenic substrate used

Ectoenzymatic activity, prokaryotic heterotrophic abundances and production were determined in the Mediterranean Sea. Sampling was carried out in the sub-surface, the deep chlorophyll maximum layer (DCM), the core of the Levantine intermediate waters and in the deeper part of the mesopelagic layers. Michaelis–Menten kinetics were assessed using a large range of concentrations of fluorogenic substrates (0.025 to 50 µM). As a consequence, Km (Michaelis–Menten half-saturation constant) and Vm (maximum hydrolysis velocity) parameters were determined for both low- and high-affinity enzymes for alkaline phosphatase, aminopeptidase (LAP) and β-glucosidase (βGLU). Based on the constant derived from the high-LAP-affinity enzyme (0.025–1 µM substrate concentration range), in situ hydrolysis of N proteins contributed 48 % ± 30 % to the heterotrophic bacterial nitrogen demand within the epipelagic layers and 180 % ± 154 % in the Levantine intermediate waters and the upper part of the mesopelagic layers. The LAP hydrolysis rate was higher than bacterial N demand only within the deeper layer and only when considering the high-affinity enzyme. Based on a 10 % bacterial growth efficiency, the cumulative hydrolysis rates of C proteins and C polysaccharides contributed on average 2.5 % ± 1.3 % to the heterotrophic bacterial carbon demand in the epipelagic layers sampled (sub-surface and DCM). This study clearly reveals potential biases in current and past interpretations of the kinetic parameters for the three enzymes tested based on the fluorogenic-substrate concentration used. In particular, the LAP / βGLU enzymatic ratios and some of the depth-related trends differed between the use of high and low concentrations of fluorogenic substrates.

Long-Term Changes in the Water Mass Properties in the Balearic Channels Over the Period 1996–2019

The analysis of a 24-year time series of Conductivity-Temperature-Depth (CTD) casts collected in the Balearic Channels (1996–2019) has allowed detecting and quantifying long-term changes in water mass properties in the Western Mediterranean. For the complete period, the intermediate waters have experienced warming and salting at rates of 1.4°C/100yr and 0.3–0.6/100yr for the Western Intermediate Water, and 1°C/100yr and 0.3–0.4/100yr for the Levantine Intermediate Water. The density of these two water masses has not changed. The deep waters, defined as those denser than 29.1 kg/m3, showed positive trends in temperature, salinity, and density (0.8°C/100yr, 0.2/100yr, and 0.02 kg.m–3/100yr, respectively). The high temporal variability of the upper layer makes the detection of long-term changes more difficult. Nevertheless, combining CTD data with temperature data from the oceanographic station at L’Estartit and simulated data from the NCEP/NCAR reanalysis, it can be established that the Atlantic Water increased its temperature at a rate of 2.1–2.8°C/100yr and likely its salinity at a rate of 0.6/100yr. The water column absorbed heat at a rate equivalent to 1–1.2 W/m2. All these trends are much higher than those reported in previous works (more than double in some cases). The warming of the water column produced an increase in the thermosteric component of sea level. However, this increase was compensated by the decrease in the halosteric component. Besides these changes, other alterations related to the Western Mediterranean Transition have been observed over shorter periods. The temperature and salinity of the intermediate waters increased before the winter of 2004/2005 and then the temperature and salinity of the deep waters increased dramatically in 2005. The density of the deep water reached values unprecedented before 2005. Deep and intermediate waters were uplifted by the presence of such dense deep waters. The arrival of warmer and saltier intermediate waters from the Eastern Mediterranean is also observed, mainly after 2010.

Cold-water corals in the Subpolar North Atlantic Ocean exposed to aragonite undersaturation if Paris 2 ºC is not met

<p>The uptake of carbon dioxide (CO<sub>2</sub>) from the atmosphere is changing the ocean’s chemical state. Such changes, commonly known as ocean acidification, include reduction in pH and the carbonate ion concentration ([CO<sub>3</sub><sup>2-</sup>]), which in turn lowers oceanic saturation states (Ω) for calcium carbonate (CaCO<sub>3</sub>) minerals. The Ω values for aragonite (Ω<sub>aragonite</sub>; one of the main CaCO<sub>3</sub> minerals formed by marine calcifying organisms) influence the calcification rate and geographic distribution of cold-water corals (CWCs), important for biodiversity. In this work we use high-quality data of inorganic carbon measurements, collected on thirteen cruises along the same track during 1991–2018, to determine the long-term trends in Ω<sub>aragonite</sub> in the Irminger and Iceland Basins of the North Atlantic Ocean, providing the first trends of Ω<sub>aragonite</sub> in the deep waters of these basins. The entire water column of both basins showed significant negative Ω<sub>aragonite</sub> trends between -0.0015 ± 0.0002 and -0.0061 ± 0.0016 per year. The decrease in Ω<sub>aragonite</sub> in the intermediate waters, where nearly half of the CWC reefs of the study region are located, caused the Ω<sub>aragonite</sub> isolines to migrate upwards rapidly at a rate between 6 and 34 m per year. The main driver of the observed decline in Ω<sub>aragonite</sub> in the Irminger and Iceland Basins was the increase in anthropogenic CO<sub>2</sub>. But this was partially offset by increases in salinity (in Subpolar Mode Water), enhanced ventilation (in upper Labrador Sea Water) and increases in alkalinity (in classical Labrador Sea Water, cLSW; and overflow waters). We also found that water mass aging reinforced the Ω<sub>aragonite</sub> decrease in cLSW. Based on the observed Ω<sub>aragonite</sub> trends, we project that the entire water column of the Irminger and Iceland Basins will likely be undersaturated for aragonite when in equilibrium with an atmospheric mole fraction of CO<sub>2</sub> (xCO<sub>2</sub>) of ~860 ppmv, corresponding to climate model projections for the end of the century based on the highest CO<sub>2</sub> emission scenarios. However, intermediate waters will likely be aragonite undersaturated when in equilibrium with an atmospheric xCO<sub>2</sub> of ~600 ppmv, an xCO<sub>2</sub> level slightly above that corresponding to 2 ºC warming, thus exposing CWCs inhabiting the intermediate waters to undersaturation for aragonite.</p>