Soil legacy nutrients contribute to the decreasing stoichiometric ratio of N and P loading from the Mississippi River Basin.

Human-induced nitrogen-phosphorus (N, P) imbalance in terrestrial ecosystems can lead to disproportionate N and P loading to aquatic ecosystems, subsequently shifting the elemental ratio in estuaries and coastal oceans and impacting both the structure and functioning of aquatic ecosystems. The N:P ratio of nutrient loading to the Gulf of Mexico from the Mississippi River Basin increased before the late 1980s driven by the enhanced usage of N fertilizer over P fertilizer, whereafter the N:P loading ratio started to decrease although the N:P ratio of fertilizer application did not exhibit a similar trend. Here, we hypothesize that different release rates of soil legacy nutrients might contribute to the decreasing N:P loading ratio. Our study used a data-model integration framework to evaluate N and P dynamics and the potential for long-term accumulation or release of internal soil nutrient legacy stores to alter the ratio of N and P transported down the rivers. We show that the longer residence time of P in terrestrial ecosystems results in a much slower release of P to coastal oceans than N. If contemporary nutrient sources were reduced or suspended, P loading sustained by soil legacy P would decrease much slower than that of N, causing a decrease in the N and P loading ratio. The longer residence time of P in terrestrial ecosystems and the increasingly important role of soil legacy nutrients as a loading source may explain the decreasing N:P loading ratio in the Mississippi River Basin. Our study underscores a promising prospect for N loading control and the urgency to integrate soil P legacy into sustainable nutrient management strategies for aquatic ecosystem health and water security.

Purified meta-Cresol Purple dye perturbation: How it influences spectrophotometric pH measurements.

Ocean acidification, a phenomenon of seawater pH decrease due to increasing atmospheric CO2, has a global effect on seawater chemistry, marine biology, and ecosystems. Ocean acidification is a gradual and global long-term process, the study of which demands high-quality pH data. The spectrophotometric technique is capable of generating accurate and precise pH measurements but requires adding an indicator dye that perturbs the sample original pH. While the perturbation is modest in well-buffered seawater, applications of the method in environments with lower buffer capacity such as riverine, estuarine, sea-ice meltwater and lacustrine environments are increasingly common, and uncertainties related to larger potential dye perturbations need further evaluation. In this paper, we assess the effect of purified meta-Cresol Purple (mCP) dye addition on the sample pH and how to correct for this dye perturbation. We conducted numerical simulations by incorporating mCP speciation into the MATLAB CO2SYS program to examine the changes in water sample pH caused by the dye addition and to reveal the dye perturbation mechanisms. Then, laboratory experiments were carried out to verify the simulation results. The simulations suggest that the dye perturbation on sample pH is a result of total alkalinity (TA) contributions from the indicator dye and chemical equilibrium shifts that are related to both the water sample properties (pH, TA, and salinity) and the indicator dye solution properties (pH and solvent matrix). The laboratory experiments supported the simulation results; the same dye solution can lead to different dye perturbations in water samples with different pH, TA, and salinity values. The modeled adjustments agreed well with the empirically determined adjustments for salinities > 5, but it showed greater errors for lower salinities with disagreements as large as 0.005 pH units. Adjustments are minimized when the pH and salinity of the dye are matched to the sample. When the dye is used over a wide range of salinity, we suggest that it should be prepared in deionized water to minimize the dye perturbation effect on pH in the fresher sample waters with less well-constrained perturbation adjustments. We also suggest that the dye perturbation correction should be based on double dye addition experiments performed over a wide range of pH, TA, and salinity. Otherwise, multiple volume dye addition experiments are recommended for each sample to determine the dye perturbation adjustment. We further create a MATLAB function dyeperturbation.m that calculates the expected dye perturbation. This function can be used to validate empirically-derived adjustments or in lieu of empirical adjustments if dye addition experiments are unfeasible (e.g., for historical data). This study of dye perturbation evaluation and correction will improve the accuracy of the pH data, necessary for monitoring the long-term anthropogenic-driven changes in the seawater carbonate system.

The changing carbon cycle of the coastal ocean.

The carbon cycle of the coastal ocean is a dynamic component of the global carbon budget. But the diverse sources and sinks of carbon and their complex interactions in these waters remain poorly understood. Here we discuss the sources, exchanges and fates of carbon in the coastal ocean and how anthropogenic activities have altered the carbon cycle. Recent evidence suggests that the coastal ocean may have become a net sink for atmospheric carbon dioxide during post-industrial times. Continued human pressures in coastal zones will probably have an important impact on the future evolution of the coastal ocean's carbon budget.

Inorganic carbon and oxygen dynamics in a marsh-dominated estuary.

We conducted a free-water mass balance-based study to address the rate of metabolism and net carbon exchange for the tidal wetland and estuarine portion of the coastal ocean and the uncertainties associated with this approach were assessed. We measured open water diurnal O2 and dissolved inorganic carbon (DIC) dynamics seasonally in a salt marsh-estuary in Georgia, U.S.A. with a focus on the marsh-estuary linkage associated with tidal flooding. We observed that the overall estuarine system was a net source of CO2 to the atmosphere and coastal ocean and a net sink for oceanic and atmospheric O2. Rates of metabolism were extremely high, with respiration (43 mol m-2 yr-1) greatly exceeding gross primary production (28 mol m-2 yr-1), such that the overall system was net heterotrophic. Metabolism measured with DIC were higher than with O2, which we attribute to high rates of anaerobic respiration and reduced sulfur storage in salt marsh sediments, and we assume substantial levels of anoxygenic photosynthesis. We found gas exchange from a flooded marsh is substantial, accounting for about 28% of total O2 and CO2 air-water exchange. A significant percentage of the overall estuarine aquatic metabolism is attributable to metabolism of marsh organisms during inundation. Our study suggests not rely on oceanographic stoichiometry to convert from O2 to C based measurements when constructing C balances for the coastal ocean. We also suggest eddy covariance measurements of salt marsh net ecosystem exchange underestimate net ecosystem production as they do not account for lateral DIC exchange associated with marsh tidal inundation.

Treated Wastewater Changes the Export of Dissolved Inorganic Carbon and Its Isotopic Composition and Leads to Acidification in Coastal Oceans.

Human-induced changes in carbon fluxes across the land-ocean interface can influence the global carbon cycle, yet the impacts of rapid urbanization and establishment of wastewater treatment plants (WWTPs) on coastal ocean carbon cycles are poorly known. This is unacceptable as at present ∼64% of global municipal wastewater is treated before discharge. Here, we report surface water dissolved inorganic carbon (DIC) and sedimentary organic carbon concentrations and their isotopic compositions in the rapidly urbanized Jiaozhou Bay in northeast China as well as carbonate parameters in effluents of three large WWTPs around the bay. Using DIC, δ13CDIC and total alkalinity (TA) data and a tracer model, we determine the contributions to DIC from wastewater DIC input, net ecosystem production, calcium carbonate precipitation, and CO2 outgassing. Our study shows that high-DIC and low-pH wastewater effluent represents an important source of DIC and acidification in coastal waters. In contrast to the traditional view of anthropogenic organic carbon export and degradation, we suggest that with the increase of wastewater discharge and treatment rates, wastewater DIC input may play an increasingly more important role in the coastal ocean carbon cycle.

CFI-rs7356506 polymorphisms associated with Vogt-Koyanagi-Harada syndrome.

PURPOSE: Complement factor I (CFI) plays an important role in complement activation pathways and is known to affect the development of uveitis. The present study was performed to investigate the existence of an association between CFI genetic polymorphisms and Vogt-Koyanagi-Harada (VKH) syndrome. METHODS: A total of 100 patients diagnosed with VKH syndrome and 300 healthy controls were recruited for the study. Two milliliters of peripheral blood were collected in a sterile anticoagulative tube. CFI-rs7356506 polymorphisms were genotyped using Sequenom MassARRAY technology. Allele and genotype frequencies were compared between patients and controls using a χ(2) test. The analyses were stratified for recurrent status, complicated cataract status, and steroid-sensitive status. RESULTS: No significant association was found between CFI-rs7356506 polymorphisms and VKH syndrome. However, patients with recurrent VKH syndrome had lower frequencies of the G allele and GG homozygosity in CFI-rs7356506 when compared to the controls (p=0.016, odds ratio [OR]=0.429, 95% confidence interval [CI]=0.212-0.871; p=0.014, OR=0.364, 95% CI=0.158-0.837, respectively). Furthermore, there were significant decreases in the frequencies of the G allele and GG homozygosity in CFI-rs7356506 in patients with VKH syndrome with complicated cataract compared to the controls (p<0.001, OR=0.357, 95% CI=0.197-0.648; p<0.001, OR=0.273, 95% CI=0.135-0.551, respectively). Nevertheless, no significant association with patients with VKH syndrome in steroid-sensitive statuses was detected for CFI-rs7356506 polymorphisms. CONCLUSIONS: Our results indicate that CFI polymorphisms are not significantly associated with VKH syndrome; nevertheless, we identified a trend for the association of CFI-7356506 with VKH syndrome that depends on the recurrent status and the complicated cataract status but not on the steroid-sensitive status.

The Formation of Aberrant Collateral Vessels during Coronary Arteriogenesis in Dog Heart.

We previously reported excessive growth of collateral vessels in the dog heart during arteriogenesis induced by implantation of an ameroid constrictor around the circumflex branch of the left coronary artery. In the present study, using histology and immunocofocal microscopy, we further investigated how these aberrant collateral vessels form. By comparison with mature collateral vessels the following findings were made: perivascular space was very narrow where damage of the perivascular myocardium occurred; the neointima was very thick, resulting in a very small lumen; elastica van Gieson staining revealed the absence of the internal elastic lamina and of elastic fibers in the adventitia, but abundant collagen in the adventitia as well as in the neointima; smooth muscle cells of the neointima expressed less α-SM actin and little desmin; expression of the fibroblast growth factors aFGF, bFGF and platelet-derived growth factor (PDGF)-AB was observed mainly in the endothelial cells and abluminal region, but transforming growth factor-ß1 was only present in the adventitia and damaged myocardium; angiogenesis in the neointima was observed in some collateral vessels expressing high levels of eNOS, and cell proliferation was mainly present in the abluminal region, but apoptosis was in the deep neointima. In conclusion, these data for the first time reveal that the formation of the aberrant collateral vessels in the dog heart involves active extracellular proteolysis and a special expression profile of growth factors, eNOS, cell proliferation and apoptosis. The finding of a narrow perivascular space and perivascular myocardial damage suggests that anatomical constraint is most likely the cause for exacerbated inward remodeling in aberrant collateral vessels in dog heart.

Eutrophication-Driven Hypoxia in the East China Sea off the Changjiang Estuary.

Coastal hypoxia is an increasingly recognized environmental issue of global concern to both the scientific community and the general public. We assessed the relative contributions from marine and terrestrially sourced organic matter that were responsible for oxygen consumption in a well-studied seasonal coastal hypoxic zone, the East China Sea off the Changjiang Estuary. Our fieldwork was conducted in August 2011 during reinstatement of a subsurface hypoxia, when we observed a continuous decline of dissolved oxygen along with production of dissolved inorganic carbon resulting from organic carbon remineralization. On the basis of a three end-member mixing model and determinations of the stable isotopic compositions of dissolved inorganic carbon (δ(13)CDIC), the end product of particulate organic carbon (POC) degradation, we quantified the δ(13)C value of the remineralized organic carbon (δ(13)COCx), which was -18.5 ± 1.0‰. This isotopic composition was very similar to the δ(13)C of marine sourced POC produced in situ (-18.5 ± 0.3‰) rather than that of the terrestrially sourced POC (-24.4 ± 0.2‰). We concluded that marine-sourced organic matter, formed by eutrophication-induced marine primary production, was the dominant oxygen consumer in the subsurface hypoxic zone in the East China Sea off the Changjiang Estuary.

An Ultrahigh Precision, High-Frequency Dissolved Inorganic Carbon Analyzer Based on Dual Isotope Dilution and Cavity Ring-Down Spectroscopy.

We present a novel method for continuous and automated shipboard measurements of dissolved inorganic carbon concentration ([DIC]) in surface water. The method is based on dual isotope dilution and cavity ring-down spectroscopy (DID-CRDS). In this method, seawater is continuously sampled and mixed with a flow of NaH(13)CO3 solution that is also enriched in deuterated water (the spike). The isotopic composition of CO2 (δ(13)C(spiked_sample)) derived from the DIC in the mixture, and the D/H ratio of the mixed water (δD(spiked_sample)), are measured by CRDS analyzers. The D/H of the water in the mixture allows accurate estimates of the mixing ratio of the sample and the spike. [DIC] of the sample is then calculated from the mixing ratio, [DI(13)C] of the spike, and δ(13)C(spiked_sample). In the laboratory, the precision of the method is <0.02% (±0.4 µmol kg(-1) when [DIC] = 2000 µmol kg(-1)). A shipboard test was conducted in the Delaware Bay and Estuary. For 2 min average [DIC], a precision of <0.03% was achieved. Measurements from the DID-CRDS showed good agreement with independent measurements of discrete samples using the well-established coulometric method (mean difference = -1.14 ± 1.68 µmol kg(-1)), and the nondispersive infrared(NDIR)-based methods (mean difference = -0.9 ± 4.73 µmol kg(-1)).

Activity-dependent regulation of release probability at excitatory hippocampal synapses: a crucial role of fragile X mental retardation protein in neurotransmission.

Transcriptional silencing of the Fmr1 gene encoding fragile X mental retardation protein (FMRP) causes fragile X syndrome (FXS), the most common form of inherited intellectual disability and the leading genetic cause of autism. FMRP has been suggested to play important roles in regulating neurotransmission and short-term synaptic plasticity at excitatory hippocampal and cortical synapses. However, the origins and mechanisms of these FMRP actions remain incompletely understood, and the role of FMRP in regulating synaptic release probability and presynaptic function remains debated. Here we used variance-mean analysis and peak-scaled nonstationary variance analysis to examine changes in both presynaptic and postsynaptic parameters during repetitive activity at excitatory CA3-CA1 hippocampal synapses in a mouse model of FXS. Our analyses revealed that loss of FMRP did not affect the basal release probability or basal synaptic transmission, but caused an abnormally elevated release probability specifically during repetitive activity. These abnormalities were not accompanied by changes in excitatory postsynaptic current kinetics, quantal size or postsynaptic α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptor conductance. Our results thus indicate that FMRP regulates neurotransmission at excitatory hippocampal synapses specifically during repetitive activity via modulation of release probability in a presynaptic manner. Our study suggests that FMRP function in regulating neurotransmitter release is an activity-dependent phenomenon that may contribute to the pathophysiology of FXS.

Precise determination of seawater calcium using isotope dilution inductively coupled plasma mass spectrometry.

We describe a method for rapid, precise and accurate determination of calcium ion (Ca(2+)) concentration in seawater using isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS). A 10 µL aliquot of seawater was spiked with an appropriate (43)Ca enriched solution for (44)Ca/(43)Ca ID-ICP-MS analyses, using an Element XR (Thermo Fisher Scientific), operated at low resolution in E-scan acquisition mode. A standard-sample bracketing technique was applied to correct for potential mass discrimination and ratio drift at every 5 samples. A precision of better than 0.05% for within-run and 0.10% for duplicate measurements of the IAPSO seawater standard was achieved using 10 µL solutions with a measuring time less than 3 minutes. Depth profiles of seawater samples collected from the Arctic Ocean basin were processed and compared with results obtained by the classic ethylene glycol tetra-acetic acid (EGTA) titration. Our new ID-ICP-MS data agreed closely with the conventional EGTA data, with the latter consistently displaying 1.5% excess Ca(2+) values, possibly due to a contribution of interference from Mg(2+) and Sr(2+) in the EGTA titration. The newly obtained Sr/Ca profiles reveal sensitive water mass mixing in the upper oceanic column to reflect ice melting in the Arctic region. This novel technique provides a tool for seawater Ca(2+) determination with small sample size, high throughput, excellent internal precision and external reproducibility.

Development of SPEEK-Coated IrOx Sensor for High-Biomass Aquatic pH Monitoring.

Instability is a key challenge for current pH sensors in practical applications, especially in aquatic environments with high biomass and redox substances. Herein, we present a novel approach that uses a highly stable IrOx sensing layer enveloped in a composite film of SPEEK doped with a silicon-stabilized ionic liquid (SP-IrOx). This design mitigates drift due to sensitive layer variations and minimizes interference from complex external conditions. After exhibiting robustness under moderately reducing conditions caused by S2-, I-, and ascorbic acid, the SP-IrOx sensor's efficacy was validated through real-time pH measurements in demanding aquatic settings. These included laboratory algal culture medium, sediment substrates, and mussel aquaculture areas. The sensor sustained accuracy and stability over extended periods of 6-8 days when compared to calibrated commercial electrodes. The deviations from reference samples were minimal, with a variance of no more than 0.03 pH units in mussel aquaculture areas (n = 17) and 0.07 pH units in an algal culture medium (n = 37). As a potentiometric, this solid-state electrode features a compact structure and low energy consumption, making it an economical and low-maintenance solution for precise pH monitoring in diverse challenging environments with high biomass and turbidity.

Carbonate Chemistry and the Potential for Acidification in Georgia Coastal Marshes and the South Atlantic Bight, USA.

In coastal regions and marginal bodies of water, the increase in partial pressure of carbon dioxide (pCO2) in many instances is greater than that of the open ocean due to terrestrial (river, estuarine, and wetland) influences, decreasing buffering capacity and/or increasing water temperatures. Coastal oceans receive freshwater from rivers and groundwater as well as terrestrial-derived organic matter, both of which have a direct influence on coastal carbonate chemistry. The objective of this research is to determine if coastal marshes in Georgia, USA, may be "hot-spots" for acidification due to enhanced inorganic carbon sources and if there is terrestrial influence on offshore acidification in the South Atlantic Bight (SAB). The results of this study show that dissolved inorganic carbon (DIC) and total alkalinity (TA) are elevated in the marshes compared to predictions from conservative mixing of the freshwater and oceanic end-members, with accompanying pH around 7.2 to 7.6 within the marshes and aragonite saturation states (ΩAr) <1. In the marshes, there is a strong relationship between the terrestrial/estuarine-derived organic and inorganic carbon and acidification. Comparisons of pH, TA, and DIC to terrestrial organic material markers, however, show that there is little influence of terrestrial-derived organic matter on shelf acidification during this period in 2014. In addition, ΩAr increases rapidly offshore, especially in drier months (July). River stream flow during 2014 was anomalously low compared to climatological means; therefore, offshore influences from terrestrial carbon could also be decreased. The SAB shelf may not be strongly influenced by terrestrial inputs to acidification during drier than normal periods; conversely, shelf waters that are well-buffered against acidification may not play a significant role in mitigating acidification within the Georgia marshes. Supplementary Information: The online version contains supplementary material available at 10.1007/s12237-023-01261-3.

The microbial carbon pump and climate change.

The ocean has been a regulator of climate change throughout the history of Earth. One key mechanism is the mediation of the carbon reservoir by refractory dissolved organic carbon (RDOC), which can either be stored in the water column for centuries or released back into the atmosphere as CO2 depending on the conditions. The RDOC is produced through a myriad of microbial metabolic and ecological processes known as the microbial carbon pump (MCP). Here, we review recent research advances in processes related to the MCP, including the distribution patterns and molecular composition of RDOC, links between the complexity of RDOC compounds and microbial diversity, MCP-driven carbon cycles across time and space, and responses of the MCP to a changing climate. We identify knowledge gaps and future research directions in the role of the MCP, particularly as a key component in integrated approaches combining the mechanisms of the biological and abiotic carbon pumps for ocean negative carbon emissions.

Interannual variability of air-water CO2 flux in a large eutrophic estuary.

Air-water CO2 fluxes in estuarine environments are characterized by high interannual variability, in part due to hydrological variability that alters estuarine carbonate chemistry through multiple physical and biogeochemical processes. To understand the relative contributions of these varied controls on interannual air-water CO2 fluxes in the mainstem Chesapeake Bay, we implemented both hindcast and scenario simulations using a coupled physical-biogeochemical model. Significant spatiotemporal variability in bay-wide fluxes was found over a 10-year period (1996-2005), where the mainstem Bay was primarily a net CO2 sink, except in drought periods. Sensitivity scenario results suggested substantial effects of riverine nutrient and organic matter (OM) inputs to CO2 flux variations. The high correlations between riverine inputs and upper-Bay fluxes were due to elevated respiration under increased OM inputs. The interannual flux variations in the lower Bay was mostly regulated by the nutrient inputs. Both nutrient and OM inputs contributed to the flux variability in the mid Bay. It is found that the interannual CO2 flux of the mainstem was most sensitive to riverine nutrient inputs associated with the hydrological changes. For each hindcast simulation we computed the ratio of organic carbon turnover time to water residence time (λ), a proxy for CO2 efflux potential, and found that the wetter periods had a relatively lower λ. The variability of mainstem CO2 fluxes can be well represented using a generic function of λ. The model results showed that higher river flows would lead to enhanced CO2 sinks into a large eutrophic estuary by promoting net autotrophy.

Reliability and Agreement of an Integrated Platform for Intelligent Visual Function Measurement.

INTRODUCTION: Phoropters are widely accepted for clinical use in refraction examination and visual function assessment. This study assessed the reliability of the new Inspection Platform of Visual Function (IPVF) in comparison with the conventional equipment phoropter (TOPCON VT-10) in visual function assessment. METHODS: This prospective study enrolled 80 eyes of 80 healthy subjects. The horizontal phoria at distance and near (Phoria_D and Phoria_N, respectively) was measured with the von Graefe method, negative/positive relative accommodation (NRA/PRA) was measured with the positive/negative lens method, and accommodative amplitude (AMP) was measured with the minus lens method. Data of three consecutive measurements with each instrument were evaluated using the intraclass correlation coefficient (ICC) for repeatability, and the agreement of the two instruments was evaluated using a Bland-Altman plot. RESULTS: The ICCs of the three consecutive measurements for phoria, NRA/PRA, and AMP using the IPVF instrument were high (0.87-0.96), indicating high repeatability. The ICCs of the three consecutive measurements using the phoropter were high (0.914-0.983) for phoria, NRA, and AMP, indicating high repeatability, while that of PRA was 0.732 (between 0.4 and 0.75), indicating acceptable repeatability. The 95% limits of agreement of phoria, NRA/PRA, and AMP were narrow, indicating good agreement between the two instruments. CONCLUSION: The repeatability of both instruments was high, and the IPVF instrument was slightly better in terms of PRA repeatability than the phoropter. The agreement of phoria, NRA/PRA, and AMP measured by the new IPVF instrument and phoropter was also satisfactory.

Nonstrabismic binocular dysfunctions (NBD) are common vision abnormalities. The relevant indicators involved in NBD are accommodative anomalies, convergence and divergence anomalies, and phoria. Convergence and divergence anomalies are disorders of binocular vision that result in either a failure of fusion or an inability to accurately integrate and stabilize retinal images from both eyes into a single representation. Phoria is the tendency of the eyes not to be directed towards the point of fixation, manifested in the absence or prevention of fusion. Measurement of accommodation and phoria are two particularly important components of comprehensive eye examination. Phoropter is widely used in ophthalmic clinics and optical stores for refraction examination and visual function assessment. It largely depends on the examiner's training, skill, and experience, which leads to high inter-examiner variability. In large-scale eye screening or busy hospital hours, examinees have to be inspected one by one using traditional instruments, which can be time consuming and tiring for optometrists, and can cause long queuing time for examinees. In this study, we evaluated the possibility of an alternative automatic diagnostic instrument for the assessment of binocular visual function. The platform is a new type of intelligent visual function inspection equipment with good reliability, and could be an alternative for clinicians to obtain visual function measurements with improved efficiency and fewer subjective errors. The use of this automatic instrument can avoid inter-examiner variability, helping to resolve the shortage problem of optometrists in China and offer a better testing service to eye examinees.

Wastewater inputs reduce the CO2 uptake by coastal oceans.

Every year a large quantity of wastewater is generated worldwide, but its influence on the carbon dioxide (CO2) uptake by coastal oceans is not well understood. Here, sea surface CO2 partial pressure (pCO2) and air-sea CO2 flux were examined in the Jiaozhou Bay (JZB), a temperate coastal bay strongly disturbed by wastewater inputs. Monthly surveys from April 2014 through March 2015 showed that surface pCO2 in the JZB substantially varied both temporally and spatially between 163 µatm and 1222 µatm, with an annual average of 573 µatm. During April-December, surface pCO2 was oversaturated with respect to the atmosphere, with high values exceeding 1000 µatm in the northeastern part of the bay, where seawater salinity was low mainly due to the inputs of wastewater with salinity close to zero. During January-March, surface pCO2 was undersaturated, with the lowest value of <200 µatm also mainly in the northeastern part because of low water temperature and strong biological production. Over an annual cycle, apparently sea surface temperature dominated the monthly variation of surface pCO2 in this shallow bay, while wastewater inputs and related biological production/respiration dominated its spatial variability. Overall, the JZB was a net CO2 source to the atmosphere, emitting 9.6 ± 10.8 mmol C m-2 d-1, unlike its adjacent western part of the Yellow Sea and most of the temperate coastal oceans which are a net CO2 sink. This was possibly associated with wastewater inputs that cause high sea surface pCO2 via direct inputs of CO2 and degradation of organic matter. Thus, from this viewpoint reducing wastewater discharge or lowering CO2 levels in discharged wastewater may be important paths to enhancing the CO2 uptake by coastal oceans in the future.

Eutrophication induced CO2-acidification of subsurface coastal waters: interactive effects of temperature, salinity, and atmospheric PCO2.

Increasing atmospheric carbon dioxide (CO(2)) is raising seawater CO(2) concentrations and thereby acidifying ocean water. But a second environmental problem, eutrophication, is also causing large CO(2) inputs into coastal waters. This occurs because anthropogenic inputs of nutrients have fueled massive algal blooms, which deplete bottom waters of oxygen (O(2)) and release CO(2) when the organic matter from these blooms is respired by bacteria. On the basis of a biogeochemical model, these CO(2) inputs are predicted to decrease current pH values by 0.25 to 1.1 units, effects that increased with decreasing temperature and salinity. Our model predictions agreed well with pH data from hypoxic zones in the northern Gulf of Mexico and Baltic Sea, two eutrophic coastal systems with large temperature and salinity differences. The modeled and measured decreases in pH are well within the range shown to adversely impact marine fauna. Model calculations show that the acidification from respiratory CO(2) inputs interacts in a complex fashion with that from increasing atmospheric CO(2) and that these pH effects can be more than additive in seawater at intermediate to higher temperatures. These interactions have important biological implications in a future world with increasing atmospheric CO(2), increasing anthropogenic inputs of nutrients, and rising temperatures from CO(2)-linked global warming.

High anti-interference ability induced by the SP/SiOx/ImIL composite film on IrOx pH electrodes.

High concentrations of redox substances in the solution may cause severe electrode potential drift, resulting in the inaccuracy of in situ measurements. Sulfide anion, a highly reductive substance, is the killer of all metal oxide electrodes because of its small size and strong surface activity. We first proposed to use SPEEK (SP) with silica-stabilized imidazole-type ionic liquid (ImIL) to fabricate a composite film (SP/SiOx/ImIL) to achieve a high anti-interference ability for metal electrodes. The composite film was especially designed to address the interference caused by sulfide anions and other small-sized anions (i.e., I-, F- and ascorbic acid). The reduced proton conductivity was restored by introducing ImIL into SPEEK matrix. Open circuit potential tests showed that the potential of the SP/SiOx/ImIL modified IrOx electrode fluctuated within 0.3 mV in 30 min continuous test at a concentration of 10-3 M Na2S, exhibiting good stability in moderately high sulfide solution. It also exhibited fast response and good reversibility. In addition, no potential drift was measured under other anions interferences. XPS survey verified that the Ir4+/Ir3+ ratio of the IrOx electrode did not change before and after application in sulfide-containing solution, indicating that the SP/SiOx/ImIL composite film has good anion isolation capacity.

Performance evaluations and applications of a δ13C-DIC analyzer in seawater and estuarine waters.

Dissolved inorganic carbon (DIC) and its stable isotope (δ13C-DIC) are important parameters for studying carbon cycling in aquatic environments. Traditional methods based on isotope-ratio mass spectrometers are labor-intensive and not easily deployable at field sites. Here we report the performance of a method that simultaneously measures DIC concentration and its stable isotope by using a CO2 extraction device and a Cavity Ring-Down Spectroscopy (CRDS) detector. A multi-port valve is used to increase sample throughput and improve precision. The instrument achieves average precisions of better than ±1.95 µmol kg-1 and ±0.06‰, respectively, for DIC and δ13C-DIC in seawater based on three injections for each sample. We also provide recommendations on how to precisely determine δ13C-DIC samples with a wide range of DIC content in different types of waters by examining injection volume and concentration effects. This technique was applied to study carbon cycling in the Delaware Estuary. It demonstrates that a simultaneous and precise determination of both DIC and δ13C-DIC is a powerful and effective approach for constraining the processes controlling aquatic carbon cycling and CO2 fluxes. Both laboratory tests and field applications confirmed that this system can be used with high precision to study carbon cycling in various aquatic environments.