The inputs of autochthonous organic carbon driven by mangroves reduce metal mobility and bioavailability in intertidal regions.

The significance of mangroves in carbon storage is widely acknowledged. However, the potential role of carbon enhancement driven by mangroves in mitigating the risk of metal exposure remains unclear. In this study, a natural mangrove reserve located in Futian was selected to investigate the potential role of autochthonous organic carbon on metal bioavailability. The presence of mangroves seemed to have little effect on the accumulations of Cu(II), Zn(II), Cr(VI/III), Pb(II), and Ni(II) in surface sediments. Metal mobility and bioavailability, however, were found to be directly influenced by the presence of mangroves. Compared with mudflat, mangrove sediments exhibited an obvious in the bioavailability of Cu(II), Zn(II), Cr(VI/III), Pb(II), and Ni(II) by 19-79 %, with the highest reduction occurring in the interior of mangroves dominated by K. obovata. Mangroves also significantly enhanced the accumulation of organic carbon in sediments, regardless of carbon components. Moreover, the results from random forest analysis further showed that autochthonous organic carbon was the most important carbon component that negatively related to metal bioavailability. In summary, this is the first study to provide a linkage between mangrove cover and increased autochthonous organic carbon input, which decreases metal bioavailability. The present data also suggest that mangroves are an efficient natural barrier to alleviate the risk of metal exposure in intertidal regions.

Selected Bacteria Are Critical for Karst River Carbon Sequestration via Integrating Multi-omics and Hydrochemistry Data.

Recalcitrant dissolved organic carbon (RDOC) produced by microbial carbon pumps (MCPs) in the ocean is crucial for carbon sequestration and regulating climate change in the history of Earth. However, the importance of microbes on RDOC formation in terrestrial aquatic systems, such as rivers and lakes, remains to be determined. By integrating metagenomic (MG) and metatranscriptomic (MT) sequencing, we defined the microbial communities and their transcriptional activities in both water and silt of a typical karst river, the Lijiang River, in Southwest China. Betaproteobacteria predominated in water, serving as the most prevalent population remodeling components of dissolved organic carbon (DOC). Binning method recovered 45 metagenome-assembled genomes (MAGs) from water and silt. Functional annotation of MAGs showed Proteobacteria was less versatile in degrading complex carbon, though cellulose and chitin utilization genes were widespread in this phylum, whereas Bacteroidetes had high potential for the utilization of macro-molecular organic carbon. Metabolic remodeling revealed that increased shared metabolites within the bacterial community are associated with increased concentration of DOC, highlighting the significance of microbial cooperation during producing and remodeling of carbon components. Beta-oxidation, leucine degradation, and mevalonate (MVA) modules were significantly positively correlated with the concentration of RDOC. Blockage of the leucine degradation pathway in Limnohabitans and UBA4660-related MAGs were associated with decreased RDOC in the karst river, while the Fluviicola-related MAG containing a complete leucine degradation pathway was positively correlated with RDOC concentration. Collectively, our study revealed the linkage between bacteria metabolic processes and carbon sequestration. This provided novel insights into the microbial roles in karst-rivers carbon sink.

Lipid Biomarker Investigation of the Delivery and Preservation of Autochthonous Organic Carbon in the Pearl River and Its Contribution to the Carbon Sink: Evidence from the Water and Surface Sediment.

The molecular composition of the lipid biomarkers in the surface water, water column, and surface sediments collected along the Pearl River was investigated to identify the mechanisms of the delivery and preservation of autochthonous organic carbon (AOC) and to estimate its contribution to the carbon sink. The spatial distribution of these lipid biomarkers showed that samples collected at high-DIC-concentration sites (DIC: dissolved inorganic carbon) had prominent aquatic autochthonous signatures, while samples collected at low-DIC-concentration sites showed greater terrestrial contributions, which were described as the DIC fertilization effects. In the summer, typically, intense precipitation and flood erosion diluted the biogeochemical composition and carried terrestrial plant detritus. Therefore, the percentage of AOC (auto%) was higher in the winter than in the summer. According to the calculation of the lipid biomarkers, the values of the auto% were 65% (winter) and 54% (summer) in the surface water, 55.9% (winter) and 44.6% (summer) in the below-surface water, and 52.1% (winter) and 43.9% (summer) in the surface sediment, which demonstrated that AOC accounted for a major portion of the TOC. Vertical variability was mainly present in sites with intense flood erosion, which resulted in the mixing and deposition of resuspended sediments. There was a positive correlation of the clay content with the auto% value and the biogeochemical composition, showing that clay adsorbed the organic carbon in the water, vertically deposited it into the sediment, and was the dominant mechanism of the vertical delivery of organic carbon (OC). According to the new karst carbon sink model, based on coupled carbonate weathering and aquatic photosynthesis, the karst carbon sink flux (CSF) in the Pearl River was 2.69 × 106 t/a which was 1.7 times the original estimation (1.58 × 106 t/a), and this did not consider the formation of AOC. This indicated that previously, the contribution of the riverine system to the global karst carbon sink may have been highly underestimated.

Organic carbon source tracing and the BCP effect in the Yangtze River and the Yellow River: Insights from hydrochemistry, carbon isotope, and lipid biomarker analyses.

Autochthonous organic carbon (AOC) formed by biological carbon pump (BCP) in surface waters may serve as a significant carbon sink. The locations, magnitudes, variations and mechanisms responsible for the terrestrial missing carbon sink by BCP are uncertain, especially in large river systems. In this study, hydrochemical characteristics, carbon isotope compositions of dissolved inorganic carbon (DIC) and organic carbon (OC), n-alkane homologues and C/N ratios of organic matter along the Yangtze River and the Yellow River were investigated to constrain the OC source and the significance of BCP effect. It was found that (1) DIC concentrations in the Yellow River were much higher than those in the Yangtze River, which was controlled primarily by the temperature effect; (2) AOC in the both rivers was characterized by lower C/N ratios and δ13CPOC values. Based on calculation of n-alkanes compounds, the AOC proportions ranged from 29 to 88% (49% on average, with a higher proportion (55%) in the rainy season than in the dry season (46%)) and 19-68% (41% on average; with a lower proportion in the rainy season (31%) than in the dry season (51%)) in the Yangtze River and the Yellow River, respectively, indicating intense aquatic production. Low dissolved CO2 concentration (6.17 µmol/L on average) of the Yangtze River limited the aquatic production and decreased the BCP effect in the dry season, indicated by lower AOC proportion. However, the BCP effect increased in the Yellow River in the dry season mainly due to the increased light penetration; (3) even in high turbidity riverine systems such as the Yellow River, the aquatic photosynthetic uptake of DIC could produce considerable AOC. These findings clearly show the formation of AOC by BCP in both the clear and high turbidity riverine systems, suggesting a potential direction for finding the terrestrial missing carbon sink.

The ballast effect controls the settling of autochthonous organic carbon in three subtropical karst reservoirs.

The change in hydrodynamics by damming facilitates the terrestrial biological­carbon-pump (BCP) effect and promotes the generation and burial of autochthonous organic carbon (OCauto). To constrain the burial fluxes of OCauto is crucial when assessing the role of inland waters in the global carbon cycle as OCauto originating mainly from weathering-derived dissolved inorganic carbon is overlooked in current global carbon budgeting. Here we examined the elemental and carbon isotopic compositions of the settling organic matter collected by sediment traps in three subtropical karst reservoirs (Hongfenghu, Pingzhai and Puding), SW China. The results show that 30- 60% of the settling OC in the studied reservoirs is autochthonous. The proportion of OCauto correlates inversely with OC's settling flux. Interestingly, Hongfenghu Reservoir, featured by the highest trophic state and POC concentration, has the highest fraction of OCauto but the lowest settling flux of OCauto among three reservoirs. The ballast effect of biogenic silica and lithogenic materials, rather than the aquatic primary productivity, is supposed to be the primary factor that governs the settling flux of OCauto in the studied reservoirs. Finally, it is estimated that the settling flux of OCauto in the three reservoirs is 47- 119 g C/m2/yr while the burial flux of OCauto is 10- 26 g C/m2/yr if assuming about 80% of OCauto is remineralized after sedimentation. This study demonstrates for the first time the role of biogenic silica and lithogenic materials' input in reservoir OC's settling which may be the further important due to the strengthening agricultural activity and the increasing fast-flow hydroelectric reservoirs.

The sensitivity of the carbon sink by coupled carbonate weathering to climate and land-use changes: Sediment records of the biological carbon pump effect in Fuxian Lake, Yunnan, China, during the past century.

Recent studies show that the carbon sink attributable to the weathering of carbonate rocks may have been greatly underestimated if the biological carbon pump (BCP) effect in transferring dissolved inorganic carbon (DIC) to organic carbon (autochthonous OC) by aquatic photoautotrophs is neglected. The uptake of DIC by aquatic photoautotrophs may reach 0.2 to 0.7 Pg C/a globally, indicating that the carbon sink by the coupled carbonate weathering with aquatic photosynthesis mechanism (CCW) may be an important control in climate change. In order to understand the sensitivity of the CCW carbon sink to changes of climate and land-use, a systematic study of modern trap and 100-year-long core sediments was conducted in Fuxian Lake, (Yunnan, SW China), the second-deepest plateau oligotrophic freshwater lake in China. It was found that (1) the autochthonous OC in the lake sediments was characterized by lower C/N ratios and higher δ13Corg. By means of an n-alkanes compound calculation, the proportions of autochthonous OC were determined to be in the range, 60-68% of all OC; (2) increase in the autochthonous OC accumulation rate (OCARauto) was accompanied by an increase in the inorganic carbon accumulation rate (ICAR) in both the trap and core sediments. In particular, the post-1950 OCARauto was estimated to be about 6.9 times that for the period, 1910-1950; (3) OCARauto in core sediments increased significantly with global warming and land-use change, from 1.06 g C m-2 yr-1 in 1910 to 21.74 g C m-2 yr-1 in 2017. The increasing carbon sink may act as a negative feedback on global warming if the trend holds for all lakes globally. This study is the first to quantify the burial flux of organic carbon generated by the BCP effect in lakes and may contribute to solving the problem of the missing carbon sink in the global carbon cycle.