Impacts assessment of nitrification inhibitors on U.S. agricultural emissions of reactive nitrogen gases.

Fertilizer-intensive agriculture leads to emissions of reactive nitrogen (Nr), posing threats to climate via nitrous oxide (N2O) and to air quality and human health via nitric oxide (NO) and ammonia (NH3) that form ozone and particulate matter (PM) downwind. Adding nitrification inhibitors (NIs) to fertilizers can mitigate N2O and NO emissions but may stimulate NH3 emissions. Quantifying the net effects of these trade-offs requires spatially resolving changes in emissions and associated impacts. We introduce an assessment framework to quantify such trade-off effects. It deploys an agroecosystem model with enhanced capabilities to predict emissions of Nr with or without the use of NIs, and a social cost of greenhouse gas to monetize the impacts of N2O on climate. The framework also incorporates reduced-complexity air quality and health models to monetize associated impacts of NO and NH3 emissions on human health downwind via ozone and PM. Evaluation of our model against available field measurements showed that it captured the direction of emission changes but underestimated reductions in N2O and overestimated increases in NH3 emissions. The model estimated that, averaged over applicable U.S. agricultural soils, NIs could reduce N2O and NO emissions by an average of 11% and 16%, respectively, while stimulating NH3 emissions by 87%. Impacts are largest in regions with moderate soil temperatures and occur mostly within two to three months of N fertilizer and NI application. An alternative estimate of NI-induced emission changes was obtained by multiplying the baseline emissions from the agroecosystem model by the reported relative changes in Nr emissions suggested from a global meta-analysis: -44% for N2O, -24% for NO and +20% for NH3. Monetized assessments indicate that on an annual scale, NI-induced harms from increased NH3 emissions outweigh (8.5-33.8 times) the benefits of reducing NO and N2O emissions in all agricultural regions, according to model-based estimates. Even under meta-analysis-based estimates, NI-induced damages exceed benefits by a factor of 1.1-4. Our study highlights the importance of considering multiple pollutants when assessing NIs, and underscores the need to mitigate NH3 emissions. Further field studies are needed to evaluate the robustness of multi-pollutant assessments.

Synergistic effects of peracetic acid and free ammonia pretreatment on anaerobic fermentation of waste activated sludge to promote short-chain fatty acid production for polyhydroxyalkanoate biosynthesis: Mechanisms and optimization.

Peracetic acid (PAA) combined with free ammonia (FA) pretreatment can be utilized to promote anaerobic fermentation (AF) of waste activated sludge (WAS) to produce short-chain fatty acids (SCFAs), and the resulting SCFAs are desirable carbon sources (C-sources) for polyhydroxyalkanoate (PHA) biosynthesis. This work aimed to determine the optimum conditions for PAA + FA pretreatment of sludge AF and the feasibility of using anaerobic fermentation liquor (AFL) for PHA production. To reveal the mechanisms of integrated pretreatment, the impacts of PAA + FA pretreatment on different stages of sludge AF and changes in the microbial community structure were explored. The experimental results showed that the maximum SCFA yield reached 491.35 ± 6.02 mg COD/g VSS on day 5 after pretreatment with 0.1 g PAA/g VSS +70 mg FA/L, which was significantly greater than that resulting from PAA or FA pretreatment alone. The mechanism analysis showed that PAA + FA pretreatment promoted sludge solubilization but strongly inhibited methanogenesis. According to the analysis of the microbial community, PAA + FA pretreatment changed the microbial community structure and promoted the enrichment of bacteria related to hydrolysis and acidification, and Proteiniclasticum, Macellibacteroides and Petrimonas became the dominant hydrolytic and acidifying bacteria. Finally, after alkali treatment, the AFL was utilized for batch-mode PHA production, and a maximum PHA yield of 55.05 wt% was achieved after five operation periods.

Reactive Force Field Molecular Dynamics Investigation of NH3 Generation Mechanism during Protein Pyrolysis Process.

The mechanism of ammonia formation during the pyrolysis of proteins in biomass is currently unclear. To further investigate this issue, this study employed the AMS 2023.104 software to select proteins (actual proteins) as the model compounds and the amino acids contained within them (assembled amino acids) as the comparative models. ReaxFF molecular dynamics simulations were conducted to explore the nitrogen transformation and NH3 generation mechanisms in three-phase products (char, tar, and gas) during protein pyrolysis. The research results revealed several key findings. Regardless of whether the model compounds are actual proteins or assembled amino acids, NH3 is the primary nitrogen-containing product during pyrolysis. However, as the temperature rises to higher levels, such as 2000 K and 2500 K, the amount of NH3 decreases significantly in the later stages of pyrolysis, indicating that it is being converted into other nitrogen-bearing species, such as HCN and N2. Simultaneously, we also observed significant differences between the pyrolysis processes of actual proteins and assembled amino acids. Notably, at 2000 K, the amount of NH3 generated from the pyrolysis of assembled amino acids was twice that of actual proteins. This discrepancy mainly stems from the inherent structural differences between proteins and amino acids. In proteins, nitrogen is predominantly present in a network-like structure (NH-N), which shields it from direct external exposure, thus requiring more energy for nitrogen to participate in pyrolysis reactions, making it more difficult for NH3 to form. Conversely, assembled amino acids can release NH3 through a simpler deamination process, leading to a significant increase in NH3 production during their pyrolysis.

Irons differently modulate bacterial guilds for leading to varied efficiencies in simultaneous nitrification and denitrification (SND) within four aerobic bioreactors.

As a novel biological wastewater nitrogen removal technology, simultaneous nitrification and denitrification (SND) has gained increasing attention. Iron, serving as a viable material, has been shown to influence nitrogen removal. However, the precise impact of iron on the SND process and microbiome remains unclear. In this study, bioreactors amended with iron of varying valences were evaluated for total nitrogen (TN) removal efficiencies under aerobic conditions. The acclimated control reactor without iron addition (NCR) exhibited high ammonia nitrogen (AN) removal efficiency (98.9%), but relatively low TN removal (78.6%) due to limited denitrification. The reactor containing zero-valent iron (Fe0R) demonstrated the highest SND rate of 92.3% with enhanced aerobic denitrification, albeit with lower AN removal (84.1%). Significantly lower SND efficiencies were observed in reactors with ferrous (Fe2R, 66.3%) and ferric (Fe3R, 58.2%) iron. Distinct bacterial communities involved in nitrogen metabolisms were detected in these bioreactors. The presence of complete ammonium oxidation (comammox) genus Nitrospira and anammox bacteria Candidatus Brocadia characterized efficient AN removal in NCR. The relatively low abundance of aerobic denitrifiers in NCR hindered denitrification. Fe0R exhibited highly abundant but low-efficiency methanotrophic ammonium oxidizers, Methylomonas and Methyloparacoccus, along with diverse aerobic denitrifiers, resulting in lower AN removal but an efficient SND process. Conversely, the presence of Fe2+/Fe3+ constrained the denitrifying community, contributing to lower TN removal efficiency via inefficient denitrification. Therefore, different valent irons modulated the strength of nitrification and denitrification through the assembly of key microbial communities, providing insight for microbiome modulation in nitrogen-rich wastewater treatment.

Modulating the Activity and SO2 Resistance of α-Fe2O3 Catalysts for NH3-SCR of NOx via Crystal Facet Engineering.

The development of Fe-based catalysts for the selective catalytic reduction of NOx by NH3 (NH3-SCR of NOx) has garnered significant attention due to their exceptional SO2 resistance. However, the influence of different sulfur-containing species (e.g., ferric sulfates and ammonium sulfates) on the NH3-SCR activity of Fe-based catalysts as well as its dependence on exposed crystal facets of Fe2O3 has not been revealed. This work disclosed that nanorod-like α-Fe2O3 (Fe2O3-NR) predominantly exposing (110) facet performed better than nanosheet-like α-Fe2O3 (Fe2O3-NS) predominantly exposing (001) facet in NH3-SCR reaction, due to the advantages of Fe2O3-NR in redox properties and surface acidity. Furthermore, the results of the SO2/H2O resistance test at a critical temperature of 250 °C, catalytic performance evaluations on Fe2O3-NR and Fe2O3-NS sulfated by SO2 + O2 or deposited with NH4HSO4 (ABS), and systematic characterization revealed that the reactivity of ammonium sulfates on Fe2O3 catalysts to NO(+O2) contributed to their improved catalytic performance, while ferric sulfates showed enhancing and inhibiting effects on NH3-SCR activity on Fe2O3-NR and Fe2O3-NS, respectively; despite this, Fe2O3-NR showed higher affinity for SO2 + O2. This work set a milestone in understanding the NH3-SCR reaction on Fe2O3 catalysts in the presence of SO2 from the aspect of crystal facet engineering.

Metabolic phenotyping reveals an emerging role of ammonia abnormality in Alzheimer's disease.

The metabolic implications in Alzheimer's disease (AD) remain poorly understood. Here, we conducted a metabolomics study on a moderately aging Chinese Han cohort (n = 1397; mean age 66 years). Conjugated bile acids, branch-chain amino acids (BCAAs), and glutamate-related features exhibited strong correlations with cognitive impairment, clinical stage, and brain amyloid-ß deposition (n = 421). These features demonstrated synergistic performances across clinical stages and subpopulations and enhanced the differentiation of AD stages beyond demographics and Apolipoprotein E ε4 allele (APOE-ε4). We validated their performances in eight data sets (total n = 7685) obtained from Alzheimer's Disease Neuroimaging Initiative (ADNI) and Religious Orders Study and Memory and Aging Project (ROSMAP). Importantly, identified features are linked to blood ammonia homeostasis. We further confirmed the elevated ammonia level through AD development (n = 1060). Our findings highlight AD as a metabolic disease and emphasize the metabolite-mediated ammonia disturbance in AD and its potential as a signature and therapeutic target for AD.

Concomitant urea stabilization and phosphorus recovery from source-separated fresh urine in magnesium anode-based peroxide-producing electrochemical cells.

In this study, we investigated the recovery of nitrogen (N) and phosphorus (P) from fresh source-separated urine with a novel electrochemical cell equipped with a magnesium (Mg) anode and carbon-based gas-diffusion cathode. Recovery of P, which exists primarily as phosphate (PO43-) in urine, was achieved through pH-driven precipitation. Maximizing N recovery requires simultaneous approaches to address urea and ammonia (NH3). NH3 recovery was possible through precipitation in struvite with soluble Mg supplied by the anode. Urea was stabilized with electrochemically synthesized hydrogen peroxide (H2O2) from the cathode. H2O2 concentrations and resulting urine pH were directly proportional to the applied current density. Concomitant NH3 and PO43- precipitation as struvite and urea stabilization via H2O2 electrosynthesis was possible at lower current densities, resulting in urine pH under 9.2. Higher current densities resulted in urine pH over 9.2, yielding higher H2O2 concentrations and more consistent stabilization of urea at the expense of NH3 recovery as struvite; PO43- precipitation still occurred but in the form of calcium phosphate and magnesium phosphate solids.

Using predictive models unravel the potential of titanium oxide-loaded activated carbon for the removal of leachate ammoniacal nitrogen.

The TiO2 nanocomposite efficiency was determined under optimized conditions with activated carbon to remove ammoniacal nitrogen (NH3-N) from the leachate sample. In this work, the facile impregnation and pyrolysis synthesis method was employed to prepare the nanocomposite, and their formation was confirmed using the FESEM, FTIR, XRD, and Raman studies. In contrast, Raman phonon mode intensity ratio ID/IG increases from 2.094 to 2.311, indicating the increase of electronic conductivity and defects with the loading of TiO2 nanoparticles. The experimental optimal conditions for achieving maximum NH3-N removal of 75.8% were found to be a pH of 7, an adsorbent mass of 1.75 mg/L, and a temperature of 30 °C, with a corresponding time of 160 min. The experimental data were effectively fitted with several isotherms (Freundlich, Hill, Khan, Redlich-Peterson, Toth, and Koble-Corrigan). The notably elevated R2 value of 0.99 and a lower ARE % of 14.61 strongly support the assertion that the pseudo-second-order model compromises a superior depiction of the NH3-N reduction process. Furthermore, an effective central composite design (CCD) of response surface methodology (RSM) was employed, and the lower RMSE value, precisely 0.45, demonstrated minimal disparity between the experimentally determined NH3-N removal percentages and those predicted by the model. The subsequent utilization of the desirability function allowed us to attain actual variable experimental conditions.

A hydrogel-modified electrochemical biosensor for the rapid detection of ammonia­nitrogen-resistant bacteria.

Ammonia­nitrogen wastewater is one of the main pollutants in the current environment. Rapid detection of microorganisms resistant to ammonia­nitrogen provides a basis for bioremediation of ammonia­nitrogen contaminated sites. This study uses electrochemical analysis for efficiently detecting of ammonia-resistant bacteria, utilizing a commercially available, low-cost screen-printed electrode (SPE) modified with agarose-based hydrogel (gel) or graphene oxide (GO). At the same time, the study employed electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV) to monitor bacterial growth, revealing Escherichia coli (E. coli) inhibition upon ammonia­nitrogen addition, while Raoultella terrigena (RN1) and Pseudomonas (RN2) exhibit tolerance. The method provides sensitivity results in <45 min, which is significantly faster than traditional methods. RN1 and RN2 exhibit promising ammonia­nitrogen removal rates, reaching up to 81 % and 92 %, respectively. This study aimed to develop an effective electrochemical method for rapidly detecting the sensitivity of microorganisms to ammonia­nitrogen. The method offers advantages such as high speed, efficiency, and cost-effectiveness, potentially providing valuable microbial resources for mitigating ammonia nitrogen wastewater pollution.

Ammonium-derived nitrous oxide is a global source in streams.

Global riverine nitrous oxide (N2O) emissions have increased more than 4-fold in the last century. It has been estimated that the hyporheic zones in small streams alone may contribute approximately 85% of these N2O emissions. However, the mechanisms and pathways controlling hyporheic N2O production in stream ecosystems remain unknown. Here, we report that ammonia-derived pathways, rather than the nitrate-derived pathways, are the dominant hyporheic N2O sources (69.6 ± 2.1%) in agricultural streams around the world. The N2O fluxes are mainly in positive correlation with ammonia. The potential N2O metabolic pathways of metagenome-assembled genomes (MAGs) provides evidence that nitrifying bacteria contain greater abundances of N2O production-related genes than denitrifying bacteria. Taken together, this study highlights the importance of mitigating agriculturally derived ammonium in low-order agricultural streams in controlling N2O emissions. Global models of riverine ecosystems need to better represent ammonia-derived pathways for accurately estimating and predicting riverine N2O emissions.

Nile tilapia (Oreochromis niloticus) show high tolerance to acute ammonia exposure but lose metabolic scope during prolonged exposure at low concentration.

Ammonia is a respiratory gas that is produced during the process of protein deamination. In the unionised form (NH3), it readily crosses biological membranes and is highly toxic to fish. In the present study we examined the effects of unionized ammonia (UIA), on the resting oxygen consumption (MO2), ventilation frequency (fV), heart rate (HR) and heart rate variability (HRV) in Nile tilapia (Oreochromis niloticus). Fish were either exposed to progressively increasing UIA concentrations, up to 97 µM over a 5 h period, or to a constant UIA level of 7 µM over a 24 h period. For both treatment groups resting MO2, HR and fV were recorded as physiological variables. Relative to the control group, the fish groups exposed to the incremental UIA levels did not exhibit significant changes in their MO2, HR and fV at UIA concentrations of 4, 10, 35, or 61 µM compared to control fish. Exposure to 97 µM UIA, however, elicited abrupt and significant downregulations (p < 0.05) in all three responses, as MO2, HR and fv decreased by 25, 54 and 76 % respectively, compared to control measurements. Heart rate became increasingly irregular with increasing UIA concentrations, and heart rate variability was significantly increased at 61 and 97 µM UIA. Prolonged exposure elicited significant changes at exposure 7 µM UIA. Standard (SMR) and maximum metabolic rate (MMR) were significantly reduced, as was the corresponding fV and HR. It is evident from this study that Nile tilapia is tolerant to short term exposure to UIA up to 61 µM but experience a significant metabolic change under conditions of prolonged UIA exposures even at low concentrations.

Microbiome structure and function in parallel full-scale aerobic granular sludge and activated sludge processes.

Aerobic granular sludge (AGS) and conventional activated sludge (CAS) are two different biological wastewater treatment processes. AGS consists of self-immobilised microorganisms that are transformed into spherical biofilms, whereas CAS has floccular sludge of lower density. In this study, we investigated the treatment performance and microbiome dynamics of two full-scale AGS reactors and a parallel CAS system at a municipal WWTP in Sweden. Both systems produced low effluent concentrations, with some fluctuations in phosphate and nitrate mainly due to variations in organic substrate availability. The microbial diversity was slightly higher in the AGS, with different dynamics in the microbiome over time. Seasonal periodicity was observed in both sludge types, with a larger shift in the CAS microbiome compared to the AGS. Groups important for reactor function, such as ammonia-oxidising bacteria (AOB), nitrite-oxidising bacteria (NOB), polyphosphate-accumulating organisms (PAOs) and glycogen-accumulating organisms (GAOs), followed similar trends in both systems, with higher relative abundances of PAOs and GAOs in the AGS. However, microbial composition and dynamics differed between the two systems at the genus level. For instance, among PAOs, Tetrasphaera was more prevalent in the AGS, while Dechloromonas was more common in the CAS. Among NOB, Ca. Nitrotoga had a higher relative abundance in the AGS, while Nitrospira was the main nitrifier in the CAS. Furthermore, network analysis revealed the clustering of the various genera within the guilds to modules with different temporal patterns, suggesting functional redundancy in both AGS and CAS. KEY POINTS: • Microbial community succession in parallel full-scale aerobic granular sludge (AGS) and conventional activated sludge (CAS) processes. • Higher periodicity in microbial community structure in CAS compared to in AGS. • Similar functional groups between AGS and CAS but different composition and dynamics at genus level.

Acute toxicity of total ammonia to Macrobrachium rosenbergii postlarvae at different salinity levels.

Nitrogen compounds, particularly ammonium, nitrite and nitrate, are a major problem in shrimp production systems. These compounds can accumulate in the aquatic environment and reach harmful or even lethal levels. Thus, monitoring the levels of nitrogenous compounds such as ammonia and studying their effects on the animals are essential. One tool used for this purpose is acute toxicity testing based on the evaluation of LC50 values. Furthermore, tools that can help improve the performance of aquatic organisms in culture are needed. The present study aimed to evaluate the effect of salinity on the toxicity of total ammonia to postlarvae of the freshwater prawn Macrobrachium rosenbergii. For this purpose, acute toxicity testing (LC50-96h) was performed using 540 postlarvae with a mean weight of 0.13 g and a mean total length of 2.47 cm, divided into 54 experimental units of two liters each. A completely randomized design in a 3×6 factorial scheme was used, combining three salinities (0, 5, and 10 g.L-1) and six total ammonia concentrations (0, 8, 16, 32, 64, and 128 mg.L-1), with three replicates per combination. The LC50 values for M. rosenbergii postlarvae at 24, 48, 72, and 96 h and their respective confidence intervals (95%) were estimated using the trimmed Spearman-Karber method. The results showed that salinities of 5 or 10 g.L-1 did not reduce the acute toxicity of total ammonia.

Unveiling unique microbial nitrogen cycling and nitrification driver in coastal Antarctica.

Largely removed from anthropogenic delivery of nitrogen (N), Antarctica has notably low levels of nitrogen. Though our understanding of biological sources of ammonia have been elucidated, the microbial drivers of nitrate (NO3-) cycling in coastal Antarctica remains poorly understood. Here, we explore microbial N cycling in coastal Antarctica, unraveling the biological origin of NO3- via oxygen isotopes in soil and lake sediment, and through the reconstruction of 1968 metagenome-assembled genomes from 29 microbial phyla. Our analysis reveals the metabolic potential for microbial N2 fixation, nitrification, and denitrification, but not for anaerobic ammonium oxidation, signifying a unique microbial N-cycling dynamic. We identify the predominance of complete ammonia oxidizing (comammox) Nitrospira, capable of performing the entire nitrification process. Their adaptive strategies to the Antarctic environment likely include synthesis of trehalose for cold stress, high substrate affinity for resource utilization, and alternate metabolic pathways for nutrient-scarce conditions. We confirm the significant role of comammox Nitrospira in the autotrophic, nitrification process via 13C-DNA-based stable isotope probing. This research highlights the crucial contribution of nitrification to the N budget in coastal Antarctica, identifying comammox Nitrospira clade B as a nitrification driver.

Epiberberine: a potential rumen microbial urease inhibitor to reduce ammonia release screened by targeting UreG.

Rumen microbial urease inhibitors have been proposed for regulating nitrogen emission and improving nitrogen utilization efficiency in ruminant livestock industry. However, studies on plant-derived natural inhibitors of rumen microbial urease are limited. Urease accessory protein UreG, plays a crucial role in facilitating urease maturation, is a new target for design of urease inhibitor. The objective of this study was to select the potential effective inhibitor of rumen microbial urease from major protoberberine alkaloids in Rhizoma Coptidis by targeting UreG. Our results showed that berberine chloride and epiberberine exerted superior inhibition potential than other alkaloids based on GTPase activity study of UreG. Berberine chloride inhibition of UreG was mixed type, while inhibition kinetics type of epiberberine was uncompetitive. Furthermore, epiberberine was found to be more effective than berberine chloride in inhibiting the combination of nickel towards UreG and inducing changes in the second structure of UreG. Molecular modeling provided the rational structural basis for the higher inhibition potential of epiberberine, amino acid residues in G1 motif and G3 motif of UreG formed interactions with D ring of berberine chloride, while interacted with A ring and D ring of epiberberine. We further demonstrated the efficacy of epiberberine in the ruminal microbial fermentation with low ammonia release and urea degradation. In conclusion, our study clearly indicates that epiberberine is a promising candidate as a safe and effective inhibitor of rumen microbial urease and provides an optimal strategy and suitable feed additive for regulating nitrogen excretion in ruminants in the future. KEY POINTS: • Epiberberine is the most effective inhibitor of rumen urease from Rhizoma Coptidis. • Urease accessory protein UreG is an effective target for design of urease inhibitor. • Epiberberine may be used as natural feed additive to reducing NH3 release in ruminants.

Nitrogen dynamics as a function of soil types, compaction, and moisture.

In this study, the complex interactions between soil types, compaction, and moisture on nitrogen (N) transformation processes such as ammonia (NH3) volatilization, ammonification, nitrification, and denitrification were examined over a 30-day period using a simulated column approach. Two soil types: loam, and sandy loam, were subjected to three compaction treatments-control, surface, and sub-surface compaction-and two moisture regimes, dry and wet. Liquid urea ammonium nitrate (32-0-0) was used as the N fertilizer source at a rate of 200 kg N ha-1. Key indicators of N transformations were measured, including residual concentrations of ammonium (NH4-N) and nitrate (NO3-N), NO3-N leaching, NH3 volatilization, and nitrous oxide (N2O) emissions. Findings revealed that compaction significantly increased residual NH4-N concentrations in deeper soil profiles, with the highest 190.80 mg kg-1 recorded in loam soil under sub-surface compaction and dry conditions. Nitrification rates decreased across both soil types due to compaction, evidenced by elevated residual NH4-N levels. Increased NO3-N leaching was observed in loam soil (178.06 mg L-1), greater than sandy loam (81.11 mg L-1), due to initial higher residual NO3- in loam soil. The interaction of compaction and moisture most affected N2O emissions, with the highest emissions in control treatments during dry weather at 2.88 kg ha -1. Additionally, higher NH3 volatilization was noted in moist sandy loam soil under control conditions at 19.64 kg ha -1. These results highlight the necessity of considering soil texture, moisture, and compaction in implementing sustainable N management strategies in agriculture and suggest recommendations such as avoiding broadcast application in moist sandy loam and loam soil to mitigate NH3 volatilization and enhance N use efficiency, as well as advocating for readjustment of fertilizer rate based on organic matter content to reduce potential NO3-N leaching and N2O emissions, particularly in loam soil.

Light-driven, bias-free nitrogenase-based bioelectrochemical cell for ammonia generation.

Nitrogen fixation is a key process that sustains life on Earth. Nitrogenase is the sole enzyme capable of fixing nitrogen under ambient conditions. Extensive research efforts have been dedicated to elucidating the enzyme mechanism and its artificial activation through high applied voltage, photochemistry, or strong reducing agents. Harnessing light irradiation to minimize the required external bias can lower the process's high energy investment. Herein, we present the development of photo-bioelectrochemical cells (PBECs) utilizing BiVO4/CoP or CdS/NiO photoanodes for nitrogenase activation toward N2 fixation. The constructed PBEC based on BiVO4/CoP photoanode requires minimal external bias (200 mV) and suppresses O2 generation that allows efficient activation of the nitrogenase enzyme, using glucose as an electron donor. In a second developed PBEC configuration, CdS/NiO photoanode was used, enabling bias-free activation of the nitrogenase-based cathode to produce 100 µM of ammonia at a faradaic efficiency (FE) of 12%. The ammonia production was determined by a commonly used fluorescence probe and further validated using 1H-NMR spectroscopy. The presented PBECs lay the foundation for biotic-abiotic systems to directly activate enzymes toward value-added chemicals by light-driven reactions.

Physiological responses of European sea bass (Dicentrarchus labrax) exposed to increased carbon dioxide and reduced seawater salinities.

BACKGROUND: The iono- and osmoregulatory capacities of marine teleosts, such as European sea bass (Dicentrarchus labrax) are expected to be challenged by high carbon dioxide exposure, and the adverse effects of elevated CO2 could be amplified when such fish migrate into less buffered hypo-osmotic estuarine environments. Therefore, the effects of increased CO2 on the physiological responses of European sea bass (Dicentrarchus labrax) acclimated to 32 ppt, 10 ppt and 2.5 ppt were investigated. METHODS: Following acclimation to different salinities for two weeks, fish were exposed to present-day (400 µatm) and future (1000 µatm) atmospheric CO2 for 1, 3, 7 and 21 days. Blood pH, plasma ions (Na+, K+, Cl-), branchial mRNA expression of ion transporters such as Na+/K+-ATPase (NKA), Na+/K+/2Cl- co-transporters (NKCC) and ammonia transporters (e.g. Rhesus glycoproteins Rhbg, Rhcg1 and Rhcg2) were examined to understand the iono- and osmoregulatory consequences of elevated CO2. RESULTS: A transient but significant increase in the blood pH of exposed fish acclimated at 10 ppt (day 1) and 2.5 ppt (day 21) was observed possibly due to an overshoot of the blood HCO3- accumulation while a significant reduction of blood pH was observed after 21 days at 2.5ppt. However, no change was seen at 32 ppt. Generally, Na + concentration of control fish was relatively higher at 10 ppt and lower at 2.5 ppt compared to 32 ppt control group at all sampling periods. Additionally, NKA was upregulated in gill of juvenile sea bass when acclimated to lower salinities compared to 32 ppt control group. CO2 exposure generally downregulated NKA mRNA expression at 32ppt (day 1), 10 ppt (days 3, 7 and 21) and 2.5ppt (days 1 and 7) and also a significant reduction of NKCC mRNA level of the exposed fish acclimated at 32 ppt (1-3 days) and 10 ppt (7-21 days) was observed. Furthermore, Rhesus glycoproteins were generally upregulated in the fish acclimated at lower salinities indicating a higher dependance on gill ammonia excretion. Increased CO2 led to a reduced expression of Rhbg and may therefore reduce ammonia excretion rate. CONCLUSION: Juvenile sea bass were relatively successful in keeping acid base balance under an ocean acidification scenario. However, this came at a cost for ionoregulation with reduced NKA, NKCC and Rhbg expression rates as a consequence.

Natural zeolite for heavy metal, ammonia removal, and physiological responses in European sea bass (Dicentrarchus labrax) juveniles tanks with different densities.

The present study aims to investigate the influence of zeolite usage and stocking densities on various parameters, including ammonia removal from water, accumulation of heavy metals in fish organs, water quality, growth performance, feed efficiency, muscle composition, as well as hematological and biochemical parameters in European seabass (Dicentrarchus labrax) over a 90-day duration. A total of 2400 D. labrax with an initial weight of 9.83 ± 2.02 g and initial length of 9.37 ± 0.32 cm were distributed among 24 tanks. The research involved six distinct treatment groups, with two different zeolite levels (0 and 15 ppt) and three stocking density levels (50, 100, and 150 fish/m3), each replicated four times. The results of the research demonstrate a statistically significant improvement (p < 0.05) in water quality measures with the introduction of zeolite. The successful implementation of this amendment mitigated the adverse effects of fish density on water quality parameters. Higher stocking density negatively impacted European sea bass growth, feed utilization, and hemato-biochemical indicators. Zeolite use effectively alleviated these adverse effects, particularly on performance, feed utilization, hematological, and biochemical parameters. The study's results indicate that the utilization of zeolite has shown to be efficacious in mitigating the accumulation of heavy metals in both water and fish organs, while concurrently augmenting fish attributes. However, the increase in density led to a significant decrease in the accumulation of heavy metals in both water and fish organs. The present study highlights the capacity of natural zeolites to mitigate the negative consequences associated with water quality concerns. The efficiency of these zeolites in limiting the accessibility of heavy metals in polluted water is shown, hence minimizing their accumulation in fish organs. In addition, the improvement of fish performance has the capacity to have a beneficial influence on both the well-being and efficiency of fish in aquaculture. Additional research is essential to fully understand the complex molecular pathways involved in utilizing natural zeolite under different fish densities.

Significance of dietary quinoa husk (Chenopodium quinoa) in gene regulation for stress mitigation in fish.

The persistent challenges posed by pollution and climate change are significant factors disrupting ecosystems, particularly aquatic environments. Numerous contaminants found in aquatic systems, such as ammonia and metal toxicity, play a crucial role in adversely affecting aquaculture production. Against this backdrop, fish feed was developed using quinoa husk (the byproduct of quinoa) as a substitute for fish meal. Six isonitrogenous diets (30%) and isocaloric diets were formulated by replacing fish meal with quinoa husk at varying percentages: 0% quinoa (control), 15, 20, 25, 30 and 35%. An experiment was conducted to explore the potential of quinoa husk in replacing fish meal and assess its ability to mitigate ammonia and arsenic toxicity as well as high-temperature stress in Pangasianodon hypophthalmus. The formulated feed was also examined for gene regulation related to antioxidative status, immunity, stress proteins, growth regulation, and stress markers. The gene regulation of sod, cat, and gpx in the liver was notably upregulated under concurrent exposure to ammonia, arsenic, and high-temperature (NH3 + As + T) stress. However, quinoa husk at 25% downregulated sod, cat, and gpx expression compared to the control group. Furthermore, genes associated with stress proteins HSP70 and DNA damage-inducible protein (DDIP) were significantly upregulated in response to stressors (NH3 + As + T), but quinoa husk at 25% considerably downregulated HSP70 and DDIP to mitigate the impact of stressors. Growth-responsive genes such as myostatin (MYST) and somatostatin (SMT) were remarkably downregulated, whereas growth hormone receptor (GHR1 and GHRß), insulin-like growth factors (IGF1X, IGF2X), and growth hormone gene were significantly upregulated with quinoa husk at 25%. The gene expression of apoptosis (Caspase 3a and Caspase 3b) and nitric oxide synthase (iNOS) were also noticeably downregulated with quinoa husk (25%) reared under stressful conditions. Immune-related gene expression, including immunoglobulin (Ig), toll-like receptor (TLR), tumor necrosis factor (TNFα), and interleukin (IL), strengthened fish immunity with quinoa husk feed. The results revealed that replacing 25% of fish meal with quinoa husk could improve the gene regulation of P. hypophthalmus involved in mitigating ammonia, arsenic, and high-temperature stress in fish.