Methylmercury biomagnification in aquatic food webs of Poyang Lake, China: Insights from amino acid signatures.

As the dominant mercury species in fish, methylmercury (MeHg) biomagnifies during its trophic transfer through aquatic food webs. MeHg is known to bind to cysteine, forming the complex of MeHg-cysteine. However, relationship between MeHg and cysteine in large-scale food webs has not been explored and contrasted with MeHg biomagnification models. Here, we quantified the compound-specific nitrogen isotopic analysis of amino acids (CSIA-AA), MeHg, and amino acid composition in aquatic organisms of Poyang Lake, the largest freshwater lake in China. The trophic positions (TPAA) of organisms ranged from 1.0 ± 0.1-3.7 ± 0.2 based on CSIA-AA approach. The trophic magnification factor (TMF) of MeHg, derived from the regression slope of Log-transformed MeHg in organisms upon their TPAA for the entire food web was 9.5 ± 0.5. Significantly positive regression between MeHg and cysteine (R2 = 0.64, p < 0.01) was documented, suggesting MeHg-cysteine complex may potentially play a critical role in the bioaccumulation of MeHg. Furthermore, TMFs of MeHg calculated with and without cysteine normalization compared well (7.7-8.7) when excluding primary producers. Our results implied that MeHg may biomagnify as the complex of MeHg-cysteine and contribute to our understanding of MeHg trophic transfer at the molecular level.

How aerosol pH responds to nitrate to sulfate ratio of fine-mode particulate.

Aerosol acidity (pH), one of key properties of fine-mode particulate (PM2.5), depends largely on nitrate and sulfate in particle. The mass contribution of nitrate relative to sulfate in PM2.5 has tended to increase in many regions globally, but how this change affects aerosol pH remains in debate. In this way, we measured PM2.5 ionic species and oxygen isotopic composition of nitrate in the eastern China, and predicted aerosol pH using the ISORROPIA-II model. When nitrate to sulfate molar ratio increases and thus PM2.5 is gradually enriched in ammonium nitrate (NH4NO3), aerosol pH tends to increase. The oxidation of nitrogen dioxide (NO2) by hydroxyl radical is responsible for most of nitrate formation (generally above 60%). These indicate that nitrate formation through gas-to-particle conversion involving ammonia and nitric acid results in increasing aerosol pH with increasing molar ratio of nitrate to sulfate. Conversely, aerosol pH is expected to decrease with increasing relative abundance of nitrate as ammonia emissions are lowered. Our research concludes that it should be considered to reduce aerosol NH4NO3 by reducing the precursors of nitric oxide and ammonia emissions, to substantially improve the air quality (i.e., reduce PM2.5 levels and potential nitrate deposition) in China.

Rayleigh based concept to track NOx emission sources in urban areas of China.

Despite the implementation of some effective measures to control emissions of nitrogen oxides (NOx = NO + NO2) in recent years, the ambient NOx concentration in urban cities of China remains high. Therefore, a quantitative understanding of NOx emission sources is critical to developing effective mediation policies. In the present study, the dual isotopic compositions of nitrate (p-NO3-) in fine-particle aerosol (PM2.5) collected daily at a regional scale (Beijing-Tianjin-Shijiazhuang) were measured to better constrain the NOx emission sources. The specific focus was on a typical haze episode that occurred simultaneously in the three urban cities (October 22-29, 2017). It was found that the nitrogen isotopic values of nitrate in PM2.5 (hereafter as δ15N-NO3-) ranged widely from -3.1‰ to + 11.4‰, with a mean value of 3.5 ± 3.7‰. Furthermore, a negative relationship between the δ15N-NO3- values and the corresponded p-NO3- concentrations during the haze period was observed. This implied the preferential formation of 15N-enriched NO3- into a fine-particle aerosol. Taking a different approach to previous publications, the Rayleigh fractionation model was used to characterize the initial isotopic signatures of ambient NOx. After accounting for the δ15N difference between p-NO3- and the source NOx, the estimated initial δ15N-NOx ranged from -20‰ to 0‰, which indicated a cosniderable contribution of non-fossil fuel emissions. The individual contributions of potential sources were further quantified using the Bayesian mixing model, revealing that NOx from coal or natural gas combustion, vehicle exhausts, biomass burning, and the microbial activity contributed 17.9 ± 11.4%, 29.4 ± 19.6%, 29.1 ± 18.9% and 23.5 ± 12.7% to NO3- in PM2.5, respectively. These results highlighted that tightening controls of gaseous NOx emissions from non-fossil sources may represent an opportunity to mitigate PM2.5 pollution in urban cities of China.

Reducing N losses through surface runoff from rice-wheat rotation by improving fertilizer management.

To better understand N runoff losses from rice-wheat rotation and demonstrate the effectiveness of improved fertilizer management in reducing N runoff losses, a field study was conducted for three consecutive rice-wheat rotations. Nitrogen losses through surface runoff were measured for five treatments, including CK without N application, C200, C300 simulating the conventional practices, CO200, and CO300. Optimum N rate was applied for C200 and CO200, and 30% of chemical fertilizer was substituted with organic fertilizer for CO200 and CO300 with respect to C200 and C300, respectively. Rice season had higher runoff coefficients than wheat season. Approximately 52% of total N was lost as NH4+-N in rice season, ranging from 21 to 83%, and in wheat season, the proportion of NO3--N in total N averaged 53% with a variation from 38 to 67%. The N treatments lost less total N in rice season (1.67-10.7 kg N ha-1) than in wheat season (1.72-17.1 kg N ha-1). These suggested that a key to controlling N runoff losses from rice-wheat rotation was to limit NO3--N accumulation in wheat season. In both seasons, N runoff losses for C200 and CO300 were lower than those for C300. CO200 better cut N losses than C200 and CO300, with 64 and 57% less N in rice and wheat seasons than C300, respectively. Compared with the conventional practices, optimum N inputs integrated with co-application of organic and chemical fertilizers could reduce N runoff losses with a better N balance under rice-wheat rotation.