Screening the release of chemicals and microplastic particles from diverse plastic consumer products into water under accelerated UV weathering conditions.

Photodegradation of plastic consumer products is known to accelerate weathering and facilitate the release of chemicals and plastic particles into the aquatic environment. However, these processes are complex. In our presented pilot study, eight plastic consumer products were leached in distilled water under strong ultraviolet (UV) light simulating eight months of Central European climate and compared to their respective dark controls (DCs). The leachates and formed plastic particles were exploratorily characterized using a range of chemical analytical tools to describe degradation and leaching processes. These techniques covered (a) microplastic analysis, showing substantial liberation of plastic particles further increased under UV exposure, (b) non-targeted mass spectrometric characterization of the leachates, revealing several hundreds of chemical features with typically only minor agreement between the UV exposure and the corresponding DCs, (c) target analysis of 71 organic analytes, of which 15 could be detected in at least one sample, and (d) metal(loid) analysis, which revealed substantial release of toxic metal(loid)s further enhanced under UV exposure. A data comparison with the US-EPA's ToxVal and ToxCast databases showed that the detected metals and organic additives might pose substantial health and environmental concerns, requiring further study and comprehensive impact assessments.

Assessing Aquatic Baseline Toxicity of Plastic-Associated Chemicals: Development and Validation of the Target Plastic Model.

We developed a Target Plastic Model (TPM) to estimate the critical plastic burden of organic toxicants in five types of plastics, namely, polydimethylsiloxane (PDMS), polyoxymethylene (POM), polyacrylate (PA), low-density polyethylene (LDPE), and polyurethane ester (PU), following the Target Lipid Model (TLM) framework. By substituting the lipid-water partition coefficient in the TLM with plastic-water partition coefficients to create TPM, we demonstrated that the biomimetic nature of these plastic phases allows for the calculation of critical plastic burdens of toxicants, similar to the notion of critical lipid burdens in TLM. Following this approach, the critical plastic burdens of baseline (n = 115), less-inert (n = 73), and reactive (n = 75) toxicants ranged from 0.17 to 51.33, 0.04 to 26.62, and 1.00 × 10-6 to 6.78 × 10-4 mmol/kg of plastic, respectively. Our study showed that PDMS, PA, POM, PE, and PU are similar to biomembranes in mimicking the passive exchange of chemicals with the water phase. Using the TPM, median lethal concentration (LC50) values for fish exposed to baseline toxicants were predicted, and the results agreed with experimental values, with RMSE ranging from 0.311 to 0.538 log unit. Similarly, for the same data set of baseline toxicants, other widely used models, including the TLM (RMSE: 0.32-0.34), ECOSAR (RMSE: 0.35), and the Abraham Solvation Model (ASM; RMSE: 0.31), demonstrated comparable agreement between experimental and predicted values. For less inert chemicals, predictions were within a factor of 5 of experimental values. Comparatively, ASM and ECOSAR showed predictions within a factor of 2 and 3, respectively. The TLM based on phospholipid had predictions within a factor of 3 and octanol within a factor of 4, indicating that the TPM's performance for less inert chemicals is comparable to these established models. Unlike these methods, the TPM requires only the knowledge of plastic bound concentration for a given plastic phase to calculate baseline toxic units, bypassing the need for extensive LC50 and plastic-water partition coefficient data, which are often limited for emerging chemicals. Taken together, the TPM can provide valuable insights into the toxicities of chemicals associated with environmental plastic phases, assisting in selecting the best polymeric phase for passive sampling and designing better passive dosing techniques for toxicity experiments.

Underway mapping of coastal seawater pH using an automated shipboard analyzer with spectrophotometric detection.

The development of field-deployable methods and instruments for the measurement of pH and other carbonate parameters is important for the assessment of the marine carbon cycle, ocean acidification and marine carbon dioxide removal techniques. In this study, a high-precision fully automated integrated syringe-pump-based environmental-water analyzer for pH (iSEA-pH) was developed. The pH is determined spectrophotometrically using purified indicator dye with a high precision (better than ±0.001) and high frequency (3.5 min/sample). For the short-term analysis, the measurement frequency was 18 h-1, which revealed pH = 7.8148 ± 0.0005 (n = 104) for aged surface seawater (S = 35) from the western Pacific. For long-term analysis, the measurement frequency was 2 h-1 for 4 days, and the results showed that pH = 7.8148 ± 0.0010 (n = 200). Three commonly used pH indicators (meta-cresol purple, thymol blue and phenol red) were purified with improved flash chromatography procedures. The autonomous iSEA-pH can automatically correct for the influence of temperature, salinity and other factors on pH measurements to achieve rapid and accurate on-site measurements, which meet the "climate" goal of the Global Ocean Acidification Observing Network (uncertainty is ±0.003). Three identical iSEA-pH systems were developed and successfully applied in mesocosm experiments and several coastal and open ocean cruises with excellent in field performance.

Development of an autonomous on-site dissolved inorganic carbon analyzer using conductometric detection.

BACKGROUND: The increase in anthropogenic CO2 concentrations in the Earth's atmosphere since the industrial revolution has resulted in an increased uptake of CO2 by the oceans, leading to ocean acidification. Dissolved Inorganic Carbon (DIC) is one of the key variables to characterize the seawater carbonate system. High quality DIC observations at a high spatial-temporal resolution is required to improve our understanding of the marine carbonate system. To meet the requirements, autonomous DIC analyzers are needed which offer a high sampling frequency, are cost-effective and have a low reagent and power consumption. RESULTS: We present the development and validation of a novel analyzer for autonomous measurements of DIC in seawater using conductometric detection. The analyzer employs a gas diffusion sequential injection approach in a "Tube In A Tube" configuration that facilitates diffusion of gaseous CO2 from an acidified sample through a gas permeable membrane into a stream of an alkaline solution. The change in conductivity in the alkaline medium is proportional to the DIC concentration of the sample and is measured using a detection cell constructed of 4 hollow brass electrodes. Physical and chemical optimizations of the analyzer yielded a sampling frequency of 4 samples h-1 using sub mL reagent volumes for each measurement. Temperature and salinity effects on DIC measurements were mathematically corrected to increase accuracy. Analytical precision of ±4.9 µmol kg-1 and ±9.7 µmol kg-1 were achieved from measurements of a DIC reference material in the laboratory and during a field deployment in the southwest Baltic Sea, respectively. SIGNIFICANCE: This study describes a simple, cost-effective, autonomous, on-site benchtop DIC analyzer capable of measuring DIC in seawater at a high temporal resolution as a step towards an underwater DIC sensor. The analyzer is able to measure a wide range of DIC concentrations in both fresh and marine waters. The achieved accuracy and precision offer an excellent opportunity to employ the analyzer for ocean acidification studies and CO2 leakage detection in the context of Carbon Capture and Storage operations.

Governance pathway for coastal eutrophication based on regime shifts in diatom-dinoflagellate composition of the Bohai and Baltic Seas.

Regime shifts in the diatom-dinoflagellate composition have occurred in the Baltic Sea (BS) and Bohai Sea (BHS) under eutrophication and have affected the entire coastal ecosystem, damaging the regulatory, provisioning, cultural, and supporting service functions of marine ecosystems. Therefore, finding a solution to restore the balance of phytoplankton community composition and mitigate eutrophication is of utmost importance. In this study, the Driver (per capita gross domestic product)-Pressure (terrestrial inputs)-State (seawater environmental parameters)-Impact (proportions of diatoms and dinoflagellates)-Response (eutrophication governance projects) framework served as a guide for our analysis of the causal relationship among various environmental components in the coastal system. The relevant data in BS and BHS spanning from the 1950s to the 2010s were collected and used to construct a diatom-dinoflagellate composition single index, which allowed us to identify the shifts in regimes (mutation points and phases) of the diatom-dinoflagellate composition and environmental factors using sequential t-test analysis. We also identified key environmental factors that moderated the diatom-dinoflagellate composition using redundancy analysis and analyzed the partial effects of the main environmental factors on the diatom-dinoflagellate composition using a generalized additive model. Finally, the regulation of the eutrophication governance investment on diatom-dinoflagellate composition was investigated. We found that (1) BS is a "time machine," with coastal eutrophication governance and regime shift of diatom-dinoflagellate composition and environmental factors two decades earlier than that in BHS; (2) in BS, the key moderation factor of diatom proportion is SiO3-Si and those of dinoflagellates are sea surface salinity and N:P ratio; in BHS, the key moderation factors of diatom proportion are PO4-P and Si:N ratio and those of dinoflagellate are dissolved inorganic nitrogen and N:P and Si:P ratios; (3) it is projected that BHS will enter its recovery phase from eutrophication after mid-2020s. In summary, the N/P/Si stoichiometric relationships should be given greater consideration, with the exception of the "dose-response" relationship in both sea areas. Our results indicate an urgent need for an improved mechanistic understanding of how phytoplankton biodiversity changes in response to changes in nutrient load and how we should ultimately deal with the challenges that arise.

Dietary exposure to sulfamethazine alters fish intestinal homeostasis and promotes resistance gene transfer.

The present study was undertaken to explore the effects of sulfamethazine (SMZ) dietary exposure on the enrichment of the intestine microbial structure, and antibiotic resistance gene (ARGs) transmission in marine medaka, with respect to antibiotic dose, duration, and sex. In male fish, a dietary exposure of 10 µg/L SMZ led to a heightened SMZ enrichment in the intestine, whereas metabolite (N-SMZ) levels were elevated at a higher exposure concentration (100 µg/L). Conversely, female fish exhibited stable levels of accumulation and metabolic rates across the exposure period. The composition of intestinal microorganisms revealed that exposure duration exerted a greater impact on the abundance and diversity of gut microbes, and microbial responses to SMZ varied across exposure time points. The expansion of Bacteroidetes and Ruegeria likely stimulated SMZ metabolism and contributed to the more balanced level of SMZ and N-SMZ observed in females. In males, short-term SMZ stress resulted in a disruption of intestinal homeostasis, while the rise in the abundance of the Fusobacteria and Propionigeniuma suggested a potential enhancement in intestinal anti-inflammatory capacity over time. Overall, female medaka exhibited greater adaptability to SMZ, and males appear to experience prolonged effects due to SMZ. A total of 11 ARGs and 5 mobile genetic elements (MGEs) were identified. Ruegeria is the main carrier of two types of MGEs (IS1247, ISSm2-Xanthob), and may serve as an indicator of ARG transmission. Therefore, it is rational to consider some fish breeding areas in natural waters as potential "reservoirs" of antibiotic resistance. This research will provide a valuable reference for the transmission of drug resistance along the food chain.

World war munitions as a source of mercury in the southwest Baltic Sea.

Mercury (Hg) fulminate was used as a primary fuse in World War (WW) munitions, and may consequently be a Hg source for impacted environments. Mercury is a conspicuous and persistent pollutant, with methylmercury (MeHg) acting as a notorious neurotoxin. Considerable amounts of munitions were intentionally dumped in the North Sea and Baltic Sea following the First and Second WWs. After more than 70 years on the seafloor many munitions have corroded and likely release explosive compounds, including Hg fulminate. The Germany coastal city of Kiel was a manufacturing centre for submarines, and accordingly a prominent target for bombing and post-war disarmament. We collected water and sediment samples around Kiel Bay to assess regional levels and quantify any Hg contamination. The munition dump site Kolberger Heide (KH) and a former anti-aircraft training center Dänisch-Nienhof are situated in Kiel Bay, and were targeted for sampling. Sediment Hg concentrations around KH were notably elevated. Average Hg concentrations in KH sediments were 125 ± 76 ng/g, compared to 14 ± 18 ng/g at background (control) sites. In contrast, dissolved Hg in the water column exhibited no site variations, all ranging between 0.8 and 2.1 pM. Methylmercury in sediments and waters did not have enhanced concentrations amongst sites (<30 pg/g and <50 fM, respectively). Sediment-water exchange experiments showed elevated Hg and MeHg fluxes (i.e. >400 pmol m-2 d-1 MeHg) at one KH location, however remaining cores had low to no Hg and MeHg output (<0-27 pmol m-2 d-1 MeHg). Thus, sediments in Kiel Bay proximate to WW munitions could harbor and form a source of Hg, however water column mixing and removal processes attenuate any discharge from the seafloor to overlying waters.

Persistent equatorial Pacific iron limitation under ENSO forcing.

Projected responses of ocean net primary productivity to climate change are highly uncertain1. Models suggest that the climate sensitivity of phytoplankton nutrient limitation in the low-latitude Pacific Ocean plays a crucial role1-3, but this is poorly constrained by observations4. Here we show that changes in physical forcing drove coherent fluctuations in the strength of equatorial Pacific iron limitation through multiple El Niño/Southern Oscillation (ENSO) cycles, but that this was overestimated twofold by a state-of-the-art climate model. Our assessment was enabled by first using a combination of field nutrient-addition experiments, proteomics and above-water hyperspectral radiometry to show that phytoplankton physiological responses to iron limitation led to approximately threefold changes in chlorophyll-normalized phytoplankton fluorescence. We then exploited the >18-year satellite fluorescence record to quantify climate-induced nutrient limitation variability. Such synoptic constraints provide a powerful approach for benchmarking the realism of model projections of net primary productivity to climate changes.

The role of seabird guano in maintaining North Atlantic summertime productivity.

Nutrients supplied via seabird guano increase primary production in some coastal ecosystems. A similar process may occur in the open ocean. To investigate this directly, we first measured bulk and leachable nutrient concentrations in guano sampled in the North Atlantic. We found that guano was strongly enriched in phosphorus, which was released as phosphate in solution. Nitrogen release was dominated by reduced forms (ammonium and urea) whilst release of nitrate was relatively low. A range of trace elements, including the micronutrient iron, were released. Using in-situ bioassays, we then showed that supply of fresh guano to ambient seawater increases phytoplankton biomass and photochemical efficiencies. Based on these results, modelled seabird distributions, and known defecation rates, we estimate that on annual scales guano is a minor source of nutrients for the surface North Atlantic. However, on shorter timescales in late spring/summer it could be much more important: Estimates of upper-level depositions of phosphorus by seabirds were three orders of magnitude higher than modelled aerosol deposition and comparable to diffusion from deeper waters.

High-Precision In Situ Total Alkalinity Analyzer Capable of Month-Long Observations in Seawaters.

Total alkalinity (TA) is an essential variable for the study of physical and biogeochemical processes in coastal and oceanic systems, and TA data obtained at high spatiotemporal resolutions are highly desired. The performance of the current in situ TA analyzers/sensors, including precision, accuracy, and deployment duration, cannot fully meet most research requirements. Here, we report on a novel high-precision in situ analyzer for surface seawater TA (ISA-TA), based on an automated single-point titration with spectrophotometric pH detection, and capable of long-term field observations. The titration was carried out in a circulating loop, where the titrant (a mixture of HCl and bromocresol green) and seawater sample were mixed in a constant volume ratio. The effect of ambient temperature on the TA measurement was corrected with an empirical formula. The weight, height, diameter, and power consumption of ISA-TA were 8.6 kg (in air), 33 cm, 20 cm, and 7.3 W, respectively. A single measurement required ∼7 min of running time, ∼32 mL of seawater, and ∼0.6 mL of titrant. ISA-TA was able to operate continuously in the field for up to 30 days, and its accuracies in the laboratory and field were 0.5 ± 1.7 µmol kg-1 (n = 13) and 10.3 ± 2.8 µmol kg-1 (n = 29) with precisions of 0.6-0.8 µmol kg-1 (n = 51) and 0.2-0.7 µmol kg-1 (n = 8), respectively. This study provides the research community with a new tool to obtain seawater TA data of high temporal resolution.

Large-scale nutrient and carbon dynamics along the river-estuary-ocean continuum.

Nutrient and carbon dynamics within the river-estuary-coastal water systems are key processes in understanding the flux of matter from the terrestrial environment to the ocean. Here, we analysed those dynamics by following a sampling approach based on the travel time of water and an advanced calculation of nutrient fluxes in the tidal part. We started with a nearly Lagrangian sampling of the river (River Elbe, Germany; 580 km within 8 days). After a subsequent investigation of the estuary, we followed the plume of the river by raster sampling the German Bight (North Sea) using three ships simultaneously. In the river, we detected intensive longitudinal growth of phytoplankton connected with high oxygen saturation and pH values and an undersaturation of CO2, whereas concentrations of dissolved nutrients declined. In the estuary, the Elbe shifted from an autotrophic to a heterotrophic system: Phytoplankton died off upstream of the salinity gradient, causing minima in oxygen saturation and pH, supersaturation of CO2, and a release of nutrients. In the shelf region, phytoplankton and nutrient concentrations were low, oxygen was close to saturation, and pH was within a typical marine range. Over all sections, oxygen saturation was positively related to pH and negatively to pCO2. Corresponding to the significant particulated nutrient flux via phytoplankton, flux rates of dissolved nutrients from river into estuary were low and determined by depleted concentrations. In contrast, fluxes from the estuary to the coastal waters were higher and the pattern was determined by tidal current. Overall, the approach is appropriate to better understand land-ocean fluxes, particularly to illuminate the importance of these fluxes under different seasonal and hydrological conditions, including flood and drought events.

Rapid shipboard measurement of net-collected marine microplastic polymer types using near-infrared hyperspectral imaging.

Isolation and detection of microplastics (MP) in marine samples is extremely cost- and labor-intensive, limiting the speed and amount of data that can be collected. In the current work, we describe rapid measurement of net-collected MPs (net mesh size 300 µm) using a benchtop near-infrared hyperspectral imaging system during a research expedition to the subtropical North Atlantic gyre. Suspected plastic particles were identified microscopically and mounted on a black adhesive background. Particles were imaged with a Specim FX17 near-infrared linescan camera and a motorized stage. A particle mapping procedure was built on existing edge-finding algorithms and a polymer identification method developed using spectra from virgin polymer reference materials. This preliminary work focused on polyethylene, polypropylene, and polystyrene as they are less dense than seawater and therefore likely to be found floating in the open ocean. A total of 27 net tows sampled 2534 suspected MP particles that were imaged and analyzed at sea. Approximately 77.1% of particles were identified as polyethylene, followed by polypropylene (9.2%). A small fraction of polystyrene was detected only at one station. Approximately 13.6% of particles were either other plastic polymers or were natural materials visually misidentified as plastics. Particle size distributions for PE and PP particles with a length greater than 1 mm followed an approximate power law relationship with abundance. This method allowed at-sea, near real-time identification of MP polymer types and particle dimensions, and shows great promise for rapid field measurements of microplastics in net-collected samples.

The Use of Bi-Potentiostat as a Simple and Accurate Electrochemical Approach for the Determination of Orthophosphate in Seawater.

Autonomous on-site monitoring of orthophosphate (PO43-), an important nutrient for primary production in natural waters, is urgently needed. Here, we report on the development and validation of an on-site autonomous electrochemical analyzer for PO43- in seawater. The approach is based on the use of flow injection analysis in conjunction with a dual electrochemical cell (i.e., a bi-potentiostat detector (FIA-DECD) that uses two working electrodes sharing the same reference and counter electrode. The two working electrodes are used (molybdate/carbon paste electrode (CPE) and CPE) to correct for matrix effects. Optimization of squarewave voltammetry parameters (including step potential, amplitude, and frequency) was undertaken to enhance analytical sensitivity. Possible interferences from non-ionic surfactants and humic acid were investigated. The limit of quantification in artificial seawater (30 g/L NaCl, pH 0.8) was 0.014 µM for a linear concentration range of 0.02-3 µM. The system used a Python script for operation and data processing. The analyzer was tested for ship-board PO43- determination during a four-day research cruise in the North Sea. The analyzer successfully measured 34 samples and achieved a good correlation (Pearson' R = 0.91) with discretely collected water samples analyzed using a laboratory-based colorimetric reference analyzer.

Effects of salinity and temperature on seawater dissolution rate of initial detonation agent mercury fulminate.

Mercury fulminate (HgFu) was used as an initial detonator for World War I and II munitions. Its presence in previously discarded and dumped munitions could potentially supply mercury pollution into coastal ecosystems where bygone weaponries reside. There is evidence that historical munitions have already contributed mercury pollution in coastal environments, and millions remain embedded in sediments and subjected to further weakening via corrosion under environmental conditions. Experiments were undertaken assessing HgFu dissolution under varying temperature and salinity conditions to constrain controls on mercury release into marine environments. Our results show that HgFu discharge is strongly temperature dependent, with dissolution rate constants increasing from ∼0.4 mg cm-2 d-1 at 5 °C to ∼2.7 mg cm-2 d-1 at 30 °C. No significant differences were observed between freshwater and seawaters up to 36 psu, except at 5 °C. These experiments provide a basis for modeling HgFu release from underwater munitions and its dynamics in coastal environments.

Phthalate esters and plastic debris abundance in the Red Sea and Sharm Obhur and their ecological risk level.

The abundance of plastic debris (PDs) and its correlation with phthalic acid esters (PAEs), a class of pollutants associated with plastics, is not well understood, although PDs have been reported in relation to the release and distribution of aquatic pollutants such as PAEs. Few studies have linked the distribution of these pollutants in seawater. The current study examined the abundance and relationship of PDs and PAEs in seawater from Sharm Obhur and the Red Sea. Estimates were also made of their ecological impacts. Sharm Obhur is a semi-enclosed bay on the eastern shore of the Red Sea, near Jeddah, Saudi Arabia, and is heavily impacted by human activities. Contaminants from Sharm Obhur may be transported into the deep waters of the Red Sea by the subsurface outflow. The PAEs concentrations in the study area ranged from 0.8 to 1224 ng/L. Among the six PAEs studied, diethyl phthalate (DEP) (22-1124 ng/L), di-n-butyl phthalate (DBP) (9-346 ng/L) and di (2-ethylhexyl) phthalate (DEHP) (62-640 ng/L) were the predominant additives detected across all the sampling sits. Whereas the other PAEs, dimethyl phthalate (DMP) (5-76 ng/L), benzyl butyl phthalate (BBP) (4-25 ng/L) and di-n-octyl phthalate DnOp (0.5-80 ng/L) were generally lower in most samples. The sum of the six analyzed PAEs (∑6 PAEs) was lower at Sharm Obhur (587 ± 82 ng/L) and in the Red Sea shelf (677 ± 182 ng/L) compared to the Red Sea shelf break (1266 ± 354 ng/L). This suggests that degradation and adsorption of PAEs were higher in Sharm Obhur and on the shelf than on the shelf break. In contrast, there was no difference in the abundance of PDs between Sharm Obhur (0.04 ± 0.02 PDs/m3), Red Sea shelf (0.05 ± 0.02 PDs/m3) and in the Red Sea shelf break (0.03 ± 0.1 PDs/m3). Polyethylene (32%) and polypropylene (8%) were dominant, mostly smaller than 5 mm2 (78%), with the majority consisting of white (52%) and black (24%) fragments (39%), fibers (35%) and films (24%). A positive correlation between PAE concentration and abundance of PDs, suggests either a common source or a causal link through leaching. The ecological risk of ∑4PAEs (DMP, DEP, DBP and DEHP) ranged from (0.20-0.78), indicating a low to moderate risk for the Red Sea. The pollution index of PDs ranged from (0.14-0.36), showing that the Sharm Obhur and both sites of Red Sea suffered relatively low pollution.

Trace metal stoichiometry of dissolved organic matter in the Amazon plume.

Dissolved organic matter (DOM) is a distinct component of Earth's hydrosphere and provides a link between the biogeochemical cycles of carbon, nutrients, and trace metals (TMs). Binding of TMs to DOM is thought to result in a TM pool with DOM-like biogeochemistry. Here, we determined elemental stoichiometries of aluminum, iron, copper, nickel, zinc, cobalt, and manganese associated with a fraction of the DOM pool isolated by solid-phase extraction at ambient pH (DOMSPE-amb) from the Amazon plume. We found that the rank order of TM stoichiometry within the DOMSPE-amb fraction was underpinned by the chemical periodicity of the TM. Furthermore, the removal of the TMSPE-amb pool at low salinity was related to the chemical hardness of the TM ion. Thus, the biogeochemistry of TMs bound to the DOMSPE-amb component in the Amazon plume was determined by the chemical nature of the TM and not by that of the DOMSPE-amb.

Phycosphere pH of unicellular nano- and micro- phytoplankton cells and consequences for iron speciation.

Surface ocean pH is declining due to anthropogenic atmospheric CO2 uptake with a global decline of ~0.3 possible by 2100. Extracellular pH influences a range of biological processes, including nutrient uptake, calcification and silicification. However, there are poor constraints on how pH levels in the extracellular microenvironment surrounding phytoplankton cells (the phycosphere) differ from bulk seawater. This adds uncertainty to biological impacts of environmental change. Furthermore, previous modelling work suggests that phycosphere pH of small cells is close to bulk seawater, and this has not been experimentally verified. Here we observe under 140 µmol photons·m-2·s-1 the phycosphere pH of Chlamydomonas concordia (5 µm diameter), Emiliania huxleyi (5 µm), Coscinodiscus radiatus (50 µm) and C. wailesii (100 µm) are 0.11 ± 0.07, 0.20 ± 0.09, 0.41 ± 0.04 and 0.15 ± 0.20 (mean ± SD) higher than bulk seawater (pH 8.00), respectively. Thickness of the pH boundary layer of C. wailesii increases from 18 ± 4 to 122 ± 17 µm when bulk seawater pH decreases from 8.00 to 7.78. Phycosphere pH is regulated by photosynthesis and extracellular enzymatic transformation of bicarbonate, as well as being influenced by light intensity and seawater pH and buffering capacity. The pH change alters Fe speciation in the phycosphere, and hence Fe availability to phytoplankton is likely better predicted by the phycosphere, rather than bulk seawater. Overall, the precise quantification of chemical conditions in the phycosphere is crucial for assessing the sensitivity of marine phytoplankton to ongoing ocean acidification and Fe limitation in surface oceans.

Improvement of On-Site Sensor for Simultaneous Determination of Phosphate, Silicic Acid, Nitrate plus Nitrite in Seawater.

Accurate, on-site determinations of macronutrients (phosphate (PO43-), nitrate (NO3-), and silicic acid (H4SiO4)) in seawater in real time are essential to obtain information on their distribution, flux, and role in marine biogeochemical cycles. The development of robust sensors for long-term on-site analysis of macronutrients in seawater is a great challenge. Here, we present improvements of a commercial automated sensor for nutrients (including PO43-, H4SiO4, and NO2- plus NO3-), suitable for a variety of aquatic environments. The sensor uses the phosphomolybdate blue method for PO43-, the silicomolybdate blue method for H4SiO4 and the Griess reagent method for NO2-, modified with vanadium chloride as reducing agent for the determination of NO3-. Here, we report the optimization of analytical conditions, including reaction time for PO43- analysis, complexation time for H4SiO4 analysis, and analyte to reagent ratio for NO3- analysis. The instrument showed wide linear ranges, from 0.2 to 100 µM PO43-, between 0.2 and 100 µM H4SiO4, from 0.5 to 100 µM NO3-, and between 0.4 and 100 µM NO2-, with detection limits of 0.18 µM, 0.15 µM, 0.45 µM, and 0.35 µM for PO43-, H4SiO4, NO3-, and NO2-, respectively. The analyzer showed good precision with a relative standard deviation of 8.9% for PO43-, 4.8% for H4SiO4, and 7.4% for NO2- plus NO3- during routine analysis of certified reference materials (KANSO, Japan). The analyzer performed well in the field during a 46-day deployment on a pontoon in the Kiel Fjord (located in the southwestern Baltic Sea), with a water supply from a depth of 1 m. The system successfully collected 443, 440, and 409 on-site data points for PO43-, Σ(NO3- + NO2-), and H4SiO4, respectively. Time series data agreed well with data obtained from the analysis of discretely collected samples using standard reference laboratory procedures and showed clear correlations with key hydrographic parameters throughout the deployment period.

Phosphorus Limitation Enhances Diazotroph Zinc Quotas.

Trichodesmium spp. is a colonial diazotrophic cyanobacterium found in the oligotrophic (sub)tropical oceans, where dissolved inorganic phosphorus (DIP) can be depleted. To cope with low P concentrations, P can be scavenged from the dissolved organic P (DOP) pool. This requires the deployment of multiple enzymes activated by trace metals, potentially enhancing metal requirements under stronger P limitations. To test this, we grew Trichodesmium under trace-metal-controlled conditions, where P was supplied as either DIP or DOP (methylphosphonic acid). Mean steady-state biomass under the DOP treatment was only 40% of that grown under equivalent DIP supply, carbon normalized alkaline phosphorus activity was elevated 4-fold, and the zinc (Zn)-carbon ratio was elevated 3.5-fold. Our finding matches the known, dominant Zn requirement across a diversity of enzymes involved in P stress responses and supports an important interaction in the oceanic cycles of these two nutrients.