N-containing dissolved organic matter promotes dissolved inorganic carbon supersaturation in the Yangtze River, China.

Dissolved inorganic carbon (DIC) represents a major global carbon pool and the flux from rivers to oceans has been observed to be increasing. The effect of weathering with respect to increasing DIC has been widely studied in recent decades; however, the influence of dissolved organic matter (DOM) on increasing DIC in large rivers remains unclear. This study employed stable carbon isotopes and Fourier transform ion cyclotron mass spectrometry (FT-ICR MS) to investigate the effect of the molecular composition of DOM on the DIC in the Yangtze River. The results showed that organic matter is an important source of DIC in the Yangtze River, accounting for 40.0 ± 12.1 % and 32.0 ± 7.2 % of DIC in wet and dry seasons, respectively, and increased along the river by approximately three times. Nitrogen (N)-containing DOM, an important composition in DOM with a percentage of ∼40 %, showed superior oxidation state than non N-containing DOM, suggesting that the presence of N could improve the degradable potential of DOM. Positive relationship between organic sourced DIC (DICOC) and N-containing DOM formulae indicated that N-containing DOM is crucial to facilitate the mineralization of DOM to DICOC. N-containg molecular formular with low H/C and O/C ratio were positively correlated with DICOC further verified these energy-rich and biolabile compounds are preferentially decomposed by bacteria to produce DIC. N-containing components significantly accelerated the degradation of DOM to DICOC, which is important for understanding the CO2 emission and carbon cycling in large rivers.

Anthropogenic Activities Generate High-Refractory Black Carbon along the Yangtze River Continuum.

Combustion-driven particulate black carbon (PBC) is a crucial slow-cycling pool in the organic carbon flux from rivers to oceans. Since the refractoriness of PBC stems from the association of non-homologous char and soot, the composition and source of char and soot must be considered when investigating riverine PBC. Samples along the Yangtze River continuum during different hydrological periods were collected in this study to investigate the association and asynchronous combustion drive of char and soot in PBC. The results revealed that PBC in the Yangtze River, with higher refractory nature, accounts for 13.73 ± 6.89% of particulate organic carbon, and soot occupies 37.53 ± 11.00% of PBC. The preponderant contribution of fossil fuel combustion to soot (92.57 ± 3.20%) compared to char (27.55 ± 5.92%), suggested that fossil fuel combustion is a crucial driver for PBC with high soot percentage. Redundancy analysis and structural equation modeling confirmed that the fossil fuel energy used by anthropogenic activities promoting soot is the crucial reason for high-refractory PBC. We estimated that the Yangtze River transported 0.15-0.23 Tg of soot and 0.15-0.25 Tg of char to the ocean annually, and the export of large higher refractory PBC to the ocean can form a long-term sink and prolong the residence time of terrigenous carbon.

Spatiotemporal response of dissolved organic matter diversity to natural and anthropogenic forces along the whole mainstream of the Yangtze River.

The Yangtze River, the largest river in Asia, plays a crucial role in linking continental and oceanic ecosystems. However, the impact of natural and anthropogenic disturbances on composition and transformation of dissolved organic matter (DOM) during long-distance transport and seasonal cycle is not fully understood. By using a combination of elemental, isotopic and optical techniques, as well as Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), we investigated DOM abundance and composition along the whole mainstream at highly spatial resolution in the dry and early wet seasons. Our findings showed that the concentration and flux of dissolved organic carbon (DOC) in the Yangtze River was much lower compared with other worldwide larger rivers. The distribution of δ13CDOC and higher abundance of humic-like fluorescent component and highly unsaturated and phenolics (HUPs) compound reflected a prominent contribution of allochthonous DOM. Further optical and molecular analysis revealed humic-like fluorescent components were coupled with CHO molecules and HUPs compound with higher aromatic, unsaturated, molecular weight and stable characteristics between upstream and midstream reaches. With increasing agricultural and urban land downstream, there were more heteroatomic formulae and labile aliphatic and protein-like compounds which were derived from human activities and in situ primary production. Meanwhile, DOM gradually accumulates with slow water flow and additional autochthonous organics. Weaker solar radiation and water dilution during the dry/cold season favours highly aromatic, unsaturated and oxygenated DOM compositions. Conversely, higher discharge during the wet/warm season diluted the terrestrial DOM, but warm temperatures could promote phytoplankton growth that releases labile aliphatic and protein-like DOM. Besides, chemical sulfurization, hydrogenation and oxygenation were found during molecular cycling processes. Our research emphasizes the active response of riverine DOM to natural and anthropogenic controls, and provides a valuable preliminary background to better understand the biogeochemical cycling of DOM in a larger river.

Nonhomologous Black Carbon Decoupled Char and Soot Sequestration Based on Stable Carbon Isotopes in Tibetan Plateau Lake Sediment.

Combustion-derived black carbon (BC) is an important component of sedimentary carbon pool. Due to different physicochemical properties, determining the source of char and soot is crucial for BC cycling, especially for nonhomologous char and soot in the Tibetan Plateau (TP). This study analyzed the sequestration and source of BC, char, and soot in the Dagze Co (inner TP) sediment core via the content and δ13C, revealing the biomass and fossil fuel driving on nonsynchronous char and soot and their response to local anthropogenic activities and atmospheric transmission. The results showed that BC concentration increased from 1.19 ± 0.35 mg g-1 (pre-1956) to 2.03 ± 1.05 mg g-1 (after 1956). The variation of char was similar to BC, while nonhomologous growth was detected in char and soot (r = 0.29 and p > 0.05). The source apportionment showed that biomass burning for 71.52 ± 10.23% of char and promoted char sequestration. The contribution of fossil fuel combustion to soot (46.67 ± 14.07%) is much higher than char (28.48 ± 10.23%). Redundancy analysis confirmed that local anthropogenic activities significantly influenced BC burial and atmospheric transport from outside TP-regulated BC burial. The contribution of biomass and fossil fuels to nonsynchronous char and soot is conducive to understanding the anthropogenic effect on BC burial in the TP.

Polycyclic aromatic hydrocarbons in remote lakes from the Tibetan Plateau: Concentrations, source, ecological risk, and influencing factors.

Polycyclic aromatic hydrocarbons (PAHs) have received worldwide attention due to their potential teratogenic, persistent, and carcinogenic characteristics. In this study, the PAHs concentrations in two dated sediment cores taken from central Tibetan Plateau (TP) were analyzed to study the deposition history, potential sources, ecological risks, and influencing factors. Total concentration of PAHs (∑PAHs) ranged from 50.0 to 195 ng g-1 and 51.9-133 ng g-1 in sediments of Pung Co (PC) and Dagze Co (DZC), respectively. 2-3-ring PAHs were dominant in the two lake sediments, accounting for an average of 77.5% and 80.1%, respectively. The historical trends of ∑PAHs in the two lakes allowed to distinguish three periods, namely, relative stability before the 1950s, a gradual increase between the 1950s and the 1990s, and then a decline to the present-day. In addition, the trend in the concentration level of each PAH composition was consistent with ∑PAHs before the 1990s, while they exhibited different trends since the 1990s, which may be the result of a combination of anthropogenic activities and climate change in recent years, whereas before the 1990s the PAH profile was mainly influenced by atmospheric deposition. The results of source apportionment examined according to diagnostic ratios and positive matrix factorization were consistent and revealed that PAHs were primarily derived from biomass and coal combustion. Significant correlations between PAHs and organic carbon (OC) indicate that OC might be a key factor influencing the concentration of PAHs in sediments. The ecological risk assessment demonstrated that PAHs in TP sediments occurred at a low risk level. Results of this study could be helpful to develop a deeper insight into the deposition history of PAHs in remote lakes of the TP region and explore the response of these variations to climate change and human activities.

Coal combustion facilitating faster burial of char than soot in a plateau lake of southwest China.

Black carbon (BC) is a retarder in carbon cycle, and the proportion of char and soot in BC restricts the significance of BC as a sink in carbon cycle. Tracing the sources of char and soot is helpful for in-depth understanding the anthropogenic-driven burial and pattern of BC, and is crucial for regulating emissions of BC and impact of BC on carbon cycle/climate change. This study investigated source-driven BC via the concentration and δ13C of BC (char and soot) in a Plateau lake sediment. The burial rate of BC (mean: 6.42 ± 5.09 g m-2 yr-1) showed an increasing trend (3.7 times after 1977 compared with before), and the growth rate of char (4.1 times) was faster than soot (2.5 times). The source trace results, showing faster growth of coal combustion ratio in char (increased 21% after 1980 compared with before) than soot (13%), proved that coal combustion promoted faster growth of char in BC. Redundancy analysis confirmed that more low-temperature utilization of coal urged a stronger driving force for char than soot, which caused BC to have lower aromatic content and higher reactivity in organic carbon pool from the past to present, further impact the effects of BC on carbon cycle.

Stable carbon isotopes trace the effect of fossil fuels on fractions of particulate black carbon in a large urban lake in China.

Black carbon (BC), the highly recalcitrant aromatic carbonaceous from the incomplete combustion of fossil fuel and biomass, is an important carbon sink in carbon cycle. Char and soot, the main components of BC, have significantly different origin and physicochemical characteristics (particle sizes and resultant transportability). The limited understanding of char and soot sources leads to poor insight into the effect of BC on carbon cycle. Sources of char and soot were investigated in this study using stable carbon isotopes to study the effect of BC on the organic carbon pool in a lake, thereby improving the knowledge of lacustrine carbon cycling. The concentration of BC in Taihu Lake ranged from 0.0 to 0.7 mg·L-1and accounted for 10.9 ± 4.7% of the particulate organic carbon. The spatial-mean δ13C values of BC, char, and soot were -23.2 ± 2.0‰, -23.5 ± 2.2‰, and -22.9 ± 1.6‰, respectively. The BC in water was primarily derived from fossil fuels (66.0 ± 9.3%), with liquid fossil fuel accounting for 48.2 ± 13.2% of the BC. The contribution of liquid fossil fuel to soot (49.3%) was much higher than that to char (36.1%); correspondingly, the contributions of biomass and coal to soot (29.2% and 21.5%) were lower than those to char (38.1% and 25.8%). The contribution of liquid fossil fuel combustion to organic carbon (OC), char, and soot gradually increased from 31.9% to 49.3%. Biomass and coal combustion primarily contributed to char (38.1% and 25.8%) and OC (37.5% and 30.6%). The source apportionment of BC, char, and soot revealed the influence of anthropogenically driven BC, char, and soot on the lake and, by extension, to the global carbon cycle.

Spatial variation of particulate black carbon, and its sources in a large eutrophic urban lake in China.

Black carbon (BC), characterized by high aromaticity and stability, has been recognized as a substantial fraction of the carbon pool in soil and sediment. The effect of BC on the particulate organic carbon (POC) pool in lake water, which is an important medium of carbon transmission and transformation, has not been thoroughly studied. The investigations of BC composition and distribution, POC, polycyclic aromatic hydrocarbons (PAHs), and stable carbon and nitrogen isotopes were conducted in a eutrophic urban lake, Taihu Lake, which is the third largest freshwater lake in China. The results indicate that the BC is composed of 55 ± 12% char and 45 ± 12% soot and accounted for 12 ± 6% of POC (the maximum value is 31%). The comparatively high levels of BC and char are distributed in the northern Taihu Lake, especially in Meiliang Bay (0.72 ± 0.38 mg L-1 and 0.45 ± 0.24 mg L-1). The distribution of soot presents a declining trend from the lakeshore to the central lake, particularly in the northern, western, and southern lakes. Source apportionment results from positive matrix factorization of PAHs suggest that consumption of fossil fuel (79 ± 20%) is the dominant source of BC, which agrees with the low ratio of char/soot (1.41 ± 0.71) and relatively depleted δ13C. The covariation of BC and PAHs and terrestrial dissolved organic carbon indicate that the effect of terrestrial input significantly regulates the distribution of BC in Taihu Lake, which is reflected in the high BC value along the lakeshore.

Source identification of particulate organic carbon using stable isotopes and n-alkanes: modeling and application.

Particulate organic carbon (POC) sources, which regulate dissolved organic carbon, sediment organic carbon, and inorganic carbon via deposition, degradation, and mineralization, play an important role in lake ecosystems. Linear or Bayesian algorithms on isotope and n-alkanes have been widely used to identify the source proportion of organic carbon. However, the applicability of these methods is ambiguous because of the unilateral advantages of each model and trace factors. To test the applicability of the various methods for identifying POC sources, we analyzed dual isotopes and n-alkanes in surface water samples of Lake Taihu, and Multi-source mixing model and Bayesian mixing model were used to distinguish between endogenous and exogenous contributions. Carbon isotope presented a clear advantage in West Taihu (-21.85 ± 0.78‰) and Southwest Taih (-22.61 ± 1.35‰); nitrogen isotope also showed high values in Meiliang Bay (9.76 ± 0.92‰). The majority of the lake was dominated by short-chain n-alkanes, except for East Taihu Lake (dominated by medium-chain n-alkanes) and areas with riverine input (dominated by long-chain n-alkanes). Different principles between the Bayesian mixing model (based on the Markov Chain Monte Carlo algorithm) and the Multi-source mixing model (based on linear estimation) caused discrepancies in the estimations of source contributions. But the fraction of chemical compounds during the migration process, and the overlap of potential sources play important role in the inconsistency of results. The estimations from the different models were consistent in indicating the dominance of endogenous organic carbon in Lake Taihu (mean of 60.18 ± 20.26%), particularly in the north and western regions (West Taihu, Meiliang Bay, and Southwest Taihu). This was likely due to algal aggregation influenced by human activities and climatic factors.