The triple oxygen isotope composition of marine sulfate and 130 million years of microbial control.

The triple oxygen isotope composition (Δ'17O) of sulfate minerals is widely used to constrain ancient atmospheric pO2/pCO2 and rates of gross primary production. The utility of this tool is based on a model that sulfate oxygen carries an isotope fingerprint of tropospheric O2 incorporated through oxidative weathering of reduced sulfur minerals, particularly pyrite. Work to date has targeted Proterozoic environments (2.5 billion to 0.542 billion years ago) where large isotope anomalies persist; younger timescale records, which would ground ancient environmental interpretation in what we know from modern Earth, are lacking. Here we present a high-resolution record of the [Formula: see text]O and Δ'17O in marine sulfate for the last 130 million years of Earth history. This record carries a Δ'17O close to 0o, suggesting that the marine sulfate reservoir is under strict control by biogeochemical cycling (namely, microbial sulfate reduction), as these reactions follow mass-dependent fractionation. We identify no discernible contribution from atmospheric oxygen on this timescale. We interpret a steady fractional contribution of microbial sulfur cycling (terrestrial and marine) over the last 100 million years, even as global weathering rates are thought to vary considerably.

Complex dynamics of coral gene expression responses to low pH across species.

Coral capacity to tolerate low pH affects coral community composition and, ultimately, reef ecosystem function. Low pH submarine discharges ('Ojo'; Yucatán, México) represent a natural laboratory to study plasticity and acclimatization to low pH in relation to ocean acidification. A previous >2-year coral transplant experiment to ambient and low pH common garden sites revealed differential survivorship across species and sites, providing a framework to compare mechanistic responses to differential pH exposures. Here, we examined gene expression responses of transplants of three species of reef-building corals (Porites astreoides, Porites porites and Siderastrea siderea) and their algal endosymbiont communities (Symbiodiniaceae) originating from low pH (Ojo) and ambient pH native origins (Lagoon or Reef). Transplant pH environment had the greatest effect on gene expression of Porites astreoides hosts and symbionts and P. porites hosts. Host P. astreoides Ojo natives transplanted to ambient pH showed a similar gene expression profile to Lagoon natives remaining in ambient pH, providing evidence of plasticity in response to ambient pH conditions. Although origin had a larger effect on host S. siderea gene expression due to differences in symbiont genera within Reef and Lagoon/Ojo natives, subtle effects of low pH on all origins demonstrated acclimatization potential. All corals responded to low pH by differentially expressing genes related to pH regulation, ion transport, calcification, cell adhesion and stress/immune response. This study demonstrates that the magnitude of coral gene expression responses to pH varies considerably among populations, species and holobionts, which could differentially affect acclimatization to and impacts of ocean acidification.

Impacts of Desalination Brine Discharge on Benthic Ecosystems.

Seawater reverse osmosis (SWRO) desalination facilities produce freshwater and, at the same time, discharge hypersaline brine that often includes various chemical additives such as antiscalants and coagulants. This dense brine can sink to the sea bottom and creep over the seabed, reaching up to 5 km from the discharge point. Previous reviews have discussed the effects of SWRO desalination brine on various marine ecosystems, yet little attention has been paid to the impacts on benthic habitats. This review comprehensibly discusses the effects of SWRO brine discharge on marine benthic fauna and flora. We review previous studies that indicated a suite of impacts by SWRO brine on benthic organisms, including bacteria, seagrasses, polychaetes, and corals. The effects within the discharge mixing zones range from impaired activities and morphological deformations to changes in the community composition. Recent modeling work demonstrated that brine could spread over the seabed, beyond the mixing zone, for up to several tens of kilometers and impair nutrient fluxes from the sediment to the water column. We also provide a possible perspective on brine's impact on the biogeochemical process within the mixing zone subsurface. Desalination brine can infiltrate into the sandy bottom around the discharge area due to gravity currents. Accumulation of brine and associated chemical additives, such as polyphosphonate-based antiscalants and ferric-based coagulants in the porewater, may change the redox zones and, hence, impact biogeochemical processes in sediments. With the demand for drinking water escalating worldwide, the volumes of brine discharge are predicted to triple during the current century. Future efforts should focus on the development and operation of viable technologies to minimize the volumes of brine discharged into marine environments, along with a change to environmentally friendly additives. However, the application of these technologies should be partly subsidized by governmental stakeholders to safeguard coastal ecosystems around desalination facilities.

A new method for phosphate purification for oxygen isotope ratio analysis in freshwater and soil extracts using solid-phase extraction with zirconium-loaded resin.

RATIONALE: Phosphate (PO4 ) oxygen isotope (δ18 OPO4 ) analysis is increasingly applied to elucidate phosphorus cycling. Due to its usefulness, analytical methods continue to be developed and improved to increase processing efficiency and applicability to various sample types. A new pretreatment procedure to obtain clean Ag3 PO4 using solid-phase extraction (SPE) with zirconium-loaded resin (ZrME), which can selectively adsorb PO4 , is presented and evaluated here. METHODS: Our method comprises (1) PO4 concentration, (2) PO4 separation by SPE, (3) cation removal, (4) Cl- removal, and (5) formation of Ag3 PO4 . The method was tested by comparing the resulting δ18 OPO4 of KH2 PO4 reagent, soil extracts (NaHCO3 , NaOH, and HCl), freshwater, and seawater with data obtained using a conventional pretreatment method. RESULTS: PO4 recovery of our method ranged from 79.2% to 97.8% for KH2 PO4 , soil extracts, and freshwater. Although the recovery rate indicated incomplete desorption of PO4 from the ZrME columns, our method produced high-purity Ag3 PO4 and accurate δ18 OPO4 values (i.e., consistent with those obtained using conventional pretreatment methods). However, for seawater, the PO4 recovery was low (1.1%), probably due to the high concentrations of F- and SO4 2- which interfere with PO4 adsorption on the columns. Experiments indicate that the ZrME columns could be regenerated and used repeatedly at least three times. CONCLUSIONS: We demonstrated the utility of ZrME for purification of PO4 from freshwater and soil extracts for δ18 OPO4 analysis. Multiple samples could be processed in three days using this method, increasing sample throughput and potentially facilitating more widespread use of δ18 OPO4 analysis to deepen our understanding of phosphorus cycling in natural environments.

Species-specific calcification response of Caribbean corals after 2-year transplantation to a low aragonite saturation submarine spring.

Coral calcification is expected to decline as atmospheric carbon dioxide concentration increases. We assessed the potential of Porites astreoides, Siderastrea siderea and Porites porites to survive and calcify under acidified conditions in a 2-year field transplant experiment around low pH, low aragonite saturation (Ωarag) submarine springs. Slow-growing S. siderea had the highest post-transplantation survival and showed increases in concentrations of Symbiodiniaceae, chlorophyll a and protein at the low Ωarag site. Nubbins of P. astreoides had 20% lower survival and higher chlorophyll a concentration at the low Ωarag site. Only 33% of P. porites nubbins survived at low Ωarag and their linear extension and calcification rates were reduced. The density of skeletons deposited after transplantation at the low Ωarag spring was 15-30% lower for all species. These results suggest that corals with slow calcification rates and high Symbiodiniaceae, chlorophyll a and protein concentrations may be less susceptible to ocean acidification, albeit with reduced skeletal density. We postulate that corals in the springs are responding to greater energy demands for overcoming larger differences in carbonate chemistry between the calcifying medium and the external environment. The differential mortality, growth rates and physiological changes may impact future coral species assemblages and the reef framework robustness.

Contributions of Atmospheric Deposition to Pb Concentration and Isotopic Composition in Seawater and Particulate Matters in the Gulf of Aqaba, Red Sea.

Lead concentrations [Pb] and isotope ratios (206Pb/207Pb, 208Pb/207Pb) have been measured in samples of total suspended particulate (TSP) aerosols, seawater, and suspended and sinking particles in the Gulf of Aqaba (GOA), Red Sea. Isotope ratios of Pb in seawater and in the soluble fraction of Pb in atmospheric TSP were similar suggesting that TSP is an important source of Pb in this area. Pb concentrations in seawater measured in this study (max 76.8 pmol kg-1) were much lower than those recorded at the same location in 2003-2004 (up to 1000 pmol kg-1). Changes in Pb isotope ratios in TSP depositions in these years indicate that leaded gasoline was responsible for the high dissolved Pb in GOA more than a decade ago and that recent regulation reduced Pb contamination. The similarity in Pb isotope ratios in suspended and sinking particles implies close interactions between these two size fractions. This study demonstrates the effect of the phasing out of leaded gasoline on TSP and seawater Pb chemistry in the Northern GOA; the rate of change in dissolved Pb concentrations in the GOA is faster than that reported for the open ocean possibly due to higher particle scavenging and the relatively short residence time of deep water in the Basin.

Identification of Phosphorus Sources in a Watershed Using a Phosphate Oxygen Isoscape Approach.

Identifying nonpoint phosphorus (P) sources in a watershed is essential for addressing cultural eutrophication and for proposing best-management solutions. The oxygen isotope ratio of phosphate (δ18OPO4) can shed light on P sources and P cycling in ecosystems. This is the first assessment of the δ18OPO4 distribution in a whole catchment, namely, the Yasu River Watershed in Japan. The observed δ18OPO4 values in the river water varied spatially from 10.3‰ to 17.6‰. To identify P sources in the watershed, we used an isoscape approach involving a multiple-linear-regression model based on land use and lithological types. We constructed two isoscape models, one using data only from the whole watershed and the other using data from the small tributaries. The model results explain 69% and 96% of the spatial variation in the river water δ18OPO4. The lower R2 value for the whole watershed model is attributed to the relatively large travel time for P in the main stream of the lower catchment that can result in cumulative biological P recycling. Isoscape maps and a correlation analysis reveal the relative importance of P loading from paddy fields and bedrock. This work demonstrates the utility of δ18OPO4 isoscape models for assessing nonpoint P sources in watershed ecosystems.

Assessing Cumulative Effects of Climate Change Manipulations on Phosphorus Limitation in a Californian Grassland.

Grasslands throughout the world are responding in diverse ways to changing climate and environmental conditions. In this study we analyze indicators of phosphorus limitation including phosphorus concentrations, phosphorus to nitrogen, and carbon ratios, oxygen isotope ratios of phosphate in vegetation, and phosphatase enzyme activity in soil to shed light on potential effects of climate change on phosphorus availability to grassland vegetation. The study was conducted at the Jasper Ridge Global Change Experiment (JRGCE), California where manipulations mimicking increases in temperature, water, nitrogen and carbon-dioxide have been maintained for over 15 years. We compare our results to an earlier study conducted 3 years after the start of the experiment, in order to assess any change in the response of phosphorus over time. Our results suggest that a decade later the measured indicators show similar or only slightly stronger responses. Specifically, addition of nitrogen, the principle parameter controlling biomass growth, increased phosphorus demand but thresholds that suggest P limitation were not reached. A study documenting changes in net primary productivity (NPP) over time at the JRGCE also could not identify a progressive effect of the manipulations on NPP. Combined these results indicate that the vegetation in these grassland systems is not very sensitive to the range of climate parameters tested.

Methane transport from the active layer to lakes in the Arctic using Toolik Lake, Alaska, as a case study.

Methane emissions in the Arctic are important, and may be contributing to global warming. While methane emission rates from Arctic lakes are well documented, methods are needed to quantify the relative contribution of active layer groundwater to the overall lake methane budget. Here we report measurements of natural tracers of soil/groundwater, radon, and radium, along with methane concentration in Toolik Lake, Alaska, to evaluate the role active layer water plays as an exogenous source for lake methane. Average concentrations of methane, radium, and radon were all elevated in the active layer compared with lake water (1.6 × 10(4) nM, 61.6 dpm⋅m(-3), and 4.5 × 10(5) dpm⋅m(-3) compared with 1.3 × 10(2) nM, 5.7 dpm⋅m(-3), and 4.4 × 10(3) dpm⋅m(-3), respectively). Methane transport from the active layer to Toolik Lake based on the geochemical tracer radon (up to 2.9 g⋅m(-2)⋅y(-1)) can account for a large fraction of methane emissions from this lake. Strong but spatially and temporally variable correlations between radon activity and methane concentrations (r(2) > 0.69) in lake water suggest that the parameters that control methane discharge from the active layer also vary. Warming in the Arctic may expand the active layer and increase the discharge, thereby increasing the methane flux to lakes and from lakes to the atmosphere, exacerbating global warming. More work is needed to quantify and elucidate the processes that control methane fluxes from the active layer to predict how this flux might change in the future and to evaluate the regional and global contribution of active layer water associated methane inputs.

Reduced calcification and lack of acclimatization by coral colonies growing in areas of persistent natural acidification.

As the surface ocean equilibrates with rising atmospheric CO2, the pH of surface seawater is decreasing with potentially negative impacts on coral calcification. A critical question is whether corals will be able to adapt or acclimate to these changes in seawater chemistry. We use high precision CT scanning of skeletal cores of Porites astreoides, an important Caribbean reef-building coral, to show that calcification rates decrease significantly along a natural gradient in pH and aragonite saturation (Ωarag). This decrease is accompanied by an increase in skeletal erosion and predation by boring organisms. The degree of sensitivity to reduced Ωarag measured on our field corals is consistent with that exhibited by the same species in laboratory CO2 manipulation experiments. We conclude that the Porites corals at our field site were not able to acclimatize enough to prevent the impacts of local ocean acidification on their skeletal growth and development, despite spending their entire lifespan in low pH, low Ωarag seawater.

Nutrient Loading through Submarine Groundwater Discharge and Phytoplankton Growth in Monterey Bay, CA.

We quantified groundwater discharge and associated nutrient fluxes to Monterey Bay, California, during the wet and dry seasons using excess (224)Ra as a tracer. Bioassay incubation experiments were conducted to document the response of bloom-forming phytoplankton to submarine groundwater discharge (SGD) input. Our data indicate that the high nutrient content (nitrate and silica) in groundwater can stimulate the growth of bloom-forming phytoplankton. The elevated concentrations of nitrate in groundwater around Monterey Bay are consistent with agriculture, landfill, and rural housing, which are the primary land-uses in the area surrounding the study site. These findings indicate that SGD acts as a continual source of nutrients that can feed bloom-forming phytoplankton at our study site, constituting a nonpoint source of anthropogenic nutrients to Monterey Bay.

Current Magnitude and Mechanisms of Groundwater Discharge in the Arctic: Case Study from Alaska.

To better understand groundwater-surface water dynamics in high latitude areas, we conducted a field study at three sites in Alaska with varying permafrost coverage. The natural groundwater tracer ((222)Rn, radon) was used to evaluate groundwater discharge, and electrical resistivity tomography (ERT) was used to examine subsurface mixing dynamics. Different controls govern groundwater discharge at these sites. In areas with sporadic permafrost (Kasitsna Bay), the major driver of submarine groundwater discharge is tidal pumping, due to the large tidal oscillations, whereas at Point Barrow, a site with continuous permafrost and small tidal amplitudes, fluxes are mostly affected by seasonal permafrost thawing. Extended areas of low resistivity in the subsurface alongshore combined with high radon in surface water suggests that groundwater-surface water interactions might enhance heat transport into deeper permafrost layers promoting permafrost thawing, thereby enhancing groundwater discharge.

Effect of temperature on photosynthesis and growth in marine Synechococcus spp.

In this study, we develop a mechanistic understanding of how temperature affects growth and photosynthesis in 10 geographically and physiologically diverse strains of Synechococcus spp. We found that Synechococcus spp. are able to regulate photochemistry over a range of temperatures by using state transitions and altering the abundance of photosynthetic proteins. These strategies minimize photosystem II (PSII) photodamage by keeping the photosynthetic electron transport chain (ETC), and hence PSII reaction centers, more oxidized. At temperatures that approach the optimal growth temperature of each strain when cellular demand for reduced nicotinamide adenine dinucleotide phosphate (NADPH) is greatest, the phycobilisome (PBS) antenna associates with PSII, increasing the flux of electrons into the ETC. By contrast, under low temperature, when slow growth lowers the demand for NADPH and linear ETC declines, the PBS associates with photosystem I. This favors oxidation of PSII and potential increase in cyclic electron flow. For Synechococcus sp. WH8102, growth at higher temperatures led to an increase in the abundance of PBS pigment proteins, as well as higher abundance of subunits of the PSII, photosystem I, and cytochrome b6f complexes. This would allow cells to increase photosynthetic electron flux to meet the metabolic requirement for NADPH during rapid growth. These PBS-based temperature acclimation strategies may underlie the larger geographic range of this group relative to Prochlorococcus spp., which lack a PBS.

Calcium isotope constraints on the end-Permian mass extinction.

The end-Permian mass extinction horizon is marked by an abrupt shift in style of carbonate sedimentation and a negative excursion in the carbon isotope (delta(13)C) composition of carbonate minerals. Several extinction scenarios consistent with these observations have been put forward. Secular variation in the calcium isotope (delta(44/40)Ca) composition of marine sediments provides a tool for distinguishing among these possibilities and thereby constraining the causes of mass extinction. Here we report delta(44/40)Ca across the Permian-Triassic boundary from marine limestone in south China. The delta(44/40)Ca exhibits a transient negative excursion of approximately 0.3 per thousand over a few hundred thousand years or less, which we interpret to reflect a change in the global delta(44/40)Ca composition of seawater. CO(2)-driven ocean acidification best explains the coincidence of the delta(44/40)Ca excursion with negative excursions in the delta(13)C of carbonates and organic matter and the preferential extinction of heavily calcified marine animals. Calcium isotope constraints on carbon cycle calculations suggest that the average delta(13)C of CO(2) released was heavier than -28 per thousand and more likely near -15 per thousand; these values indicate a source containing substantial amounts of mantle- or carbonate-derived carbon. Collectively, the results point toward Siberian Trap volcanism as the trigger of mass extinction.

Global Quaternary Carbonate Burial: Proxy- and Model-Based Reconstructions and Persisting Uncertainties.

Constraining rates of marine carbonate burial through geologic time is critical for interpreting reconstructed changes in ocean chemistry and understanding feedbacks and interactions between Earth's carbon cycle and climate. The Quaternary Period (the past 2.6 million years) is of particular interest due to dramatic variations in sea level that periodically exposed and flooded areas of carbonate accumulation on the continental shelf, likely impacting the global carbonate budget and atmospheric carbon dioxide. These important effects remain poorly quantified. Here, we summarize the importance of carbonate burial in the ocean-climate system, review methods for quantifying carbonate burial across depositional environments, discuss advances in reconstructing Quaternary carbonate burial over the past three decades, and identify gaps and challenges in reconciling the existing records. Emerging paleoceanographic proxies such as the stable strontium and calcium isotope systems, as well as innovative modeling approaches, are highlighted as new opportunities to produce continuous records of global carbonate burial.

Enhanced solubility and ecological impact of atmospheric phosphorus deposition upon extended seawater exposure.

Atmospheric P solubility affects the amount of P available for phytoplankton in the surface ocean, yet our understanding of the timing and extent of atmospheric P solubility is based on short-term leaching experiments where conditions may differ substantially from the surface ocean. We conducted longer- term dissolution experiments of atmospheric aerosols in filtered seawater, and found up to 9-fold greater dissolution of P after 72 h compared to instantaneous leaching. Samples rich in anthropogenic materials released dissolved inorganic P (DIP) faster than mineral dust. To gauge the effect of biota on the fate of atmospheric P, we conducted field incubations with aerosol samples collected in the Sargasso Sea and Red Sea. In the Sargasso Sea phytoplankton were not P limited, and biological activity enhanced DIP release from aerosols, and aerosols induced biological mineralization of dissolved organic P in seawater, leading to DIP accumulation. However, in the Red Sea where phytoplankton were colimited by P and N, soluble P was rapidly consumed by phytoplankton following aerosol enrichment. Our results suggest that atmospheric P dissolution could continue over multiple days once reaching the surface ocean, and that previous estimates of atmospheric P deposition may underestimate the contribution from this source.

Toxicity of atmospheric aerosols on marine phytoplankton.

Atmospheric aerosol deposition is an important source of nutrients and trace metals to the open ocean that can enhance ocean productivity and carbon sequestration and thus influence atmospheric carbon dioxide concentrations and climate. Using aerosol samples from different back trajectories in incubation experiments with natural communities, we demonstrate that the response of phytoplankton growth to aerosol additions depends on specific components in aerosols and differs across phytoplankton species. Aerosol additions enhanced growth by releasing nitrogen and phosphorus, but not all aerosols stimulated growth. Toxic effects were observed with some aerosols, where the toxicity affected picoeukaryotes and Synechococcus but not Prochlorococcus. We suggest that the toxicity could be due to high copper concentrations in these aerosols and support this by laboratory copper toxicity tests preformed with Synechococcus cultures. However, it is possible that other elements present in the aerosols or unknown synergistic effects between these elements could have also contributed to the toxic effect. Anthropogenic emissions are increasing atmospheric copper deposition sharply, and based on coupled atmosphere-ocean calculations, we show that this deposition can potentially alter patterns of marine primary production and community structure in high aerosol, low chlorophyll areas, particularly in the Bay of Bengal and downwind of South and East Asia.

Spatial variability in nitrification rates and ammonia-oxidizing microbial communities in the agriculturally impacted Elkhorn Slough estuary, California.

Ammonia oxidation-the microbial oxidation of ammonia to nitrite and the first step in nitrification-plays a central role in nitrogen cycling in coastal and estuarine systems. Nevertheless, questions remain regarding the connection between this biogeochemical process and the diversity and abundance of the mediating microbial community. In this study, we measured nutrient fluxes and rates of sediment nitrification in conjunction with the diversity and abundance of ammonia-oxidizing archaea (AOA) and ammonia-oxidizing betaproteobacteria (ß-AOB). Sediments were examined from four sites in Elkhorn Slough, a small agriculturally impacted coastal California estuary that opens into Monterey Bay. Using an intact sediment core flowthrough incubation system, we observed significant correlations among NO(3)(-), NO(2)(-), NH(4)(+), and PO(4)(3+) fluxes, indicating a tight coupling of sediment biogeochemical processes. (15)N-based measurements of nitrification rates revealed higher rates at the less impacted, lower-nutrient sites than at the more heavily impacted, nutrient-rich sites. Quantitative PCR analyses revealed that ß-AOB amoA (encoding ammonia monooxygenase subunit A) gene copies outnumbered AOA amoA gene copies by factors ranging from 2- to 236-fold across the four sites. Sites with high nitrification rates primarily contained marine/estuarine Nitrosospira-like bacterial amoA sequences and phylogenetically diverse archaeal amoA sequences. Sites with low nitrification rates were dominated by estuarine Nitrosomonas-like amoA sequences and archaeal amoA sequences similar to those previously described in soils. This is the first report measuring AOA and ß-AOB amoA abundance in conjunction with (15)N-based nitrification rates in estuary sediments.

The Response of Airborne Mycobiome to Dust Storms in the Eastern Mediterranean.

Airborne microbial communities directly impact the health of humans, animals, plants, and receiving ecosystems. While airborne bacterial and fungal communities have been studied by both cultivation-based methods and metabarcoding surveys targeting specific molecular markers, fewer studies have used shotgun metagenomics to study the airborne mycobiome. We analyzed the diversity and relative abundance of fungi in nine airborne metagenomes collected on clear days ("background") and during dust storms in the Eastern Mediterranean. The negative correlation between the relative abundance of fungal reads and the concentrations of atmospheric particulate matter having an aerodynamic diameter smaller than 10 µm (PM10) indicate that dust storms lower the proportion of fungi in the airborne microbiome, possibly due to the lower relative abundance of fungi in the dust storm source regions and/or more effective transport of bacteria by the dust. Airborne fungal community composition was altered by the dust storms, particularly those originated from Syria, which was enriched with xerophilic fungi. We reconstructed a high-quality fungal metagenome-assembled genome (MAG) from the order Cladosporiales, which include fungi known to adapt to environmental extremes commonly faced by airborne microbes. The negative correlation between the relative abundance of Cladosporiales MAG and PM10 concentrations indicate that its origin is dominated by local sources and likely includes the indoor environments found in the city.