Biogeochemical Cycles Of Carbon Research Articles

Spatiotemporal dynamics of dissolved organic matter and disinfection by-products formation potential of Shengzhong Lake in southwest China.

The quality and quantity of dissolved organic matter (DOM) in lakes as well as its environmental effects associated with the unintended disinfection by-products (DBPs) have received continuous attention. This work investigated the spatiotemporal dynamics of DOM in Shengzhong Lake in southwest China and the formed DBPs during the chlorine disinfection process. The results showed that lake water in summer had significantly higher dissolved oxygen and dissolved organic carbon than that in winter. In contrast, DOM in winter demonstrated an obviously higher aromaticity and molecular weight than that in summer. Four fluorescence components, i.e., terrestrial humic-like substances (C1), protein-like substances (C2), and microbial humic-like substances (C3 and C4), were identified, and their relative abundance followed in the order of C3 > C4 > C2 > C1 in winter and C4 > C3 > C1 > C2 in summer. The formation potential of trihalomethanes and haloacetic acids in winter was higher and lower than that in summer, which was mainly ascribed to the content of aromatic and hydrophobic substances. Compared to the significant seasonal dynamic, the spatial variation of DOM and the formed DBPs was not obvious. This work sheds light on the spatial-temporal distribution of DOM and the potentially formed DBPs in Shengzhong Lake, and will be helpful for understanding the biogeochemical cycle of carbon and assessing the drinking water safety.

The impacts of water-sediment regulation on organic carbon in the Yellow River

The Yellow River water-sediment regulation (WSR) is a unique hydraulic engineering project that involves the resuspension and rapid discharge of sediment downstream under the influence of density currents. This process leads to short-term high-intensity sediment scouring, which in turn increases the output of organic carbon. The impact of WSR on the biogeochemical cycling of organic carbon in rivers has not been adequately explored. In this study, we applied stable isotope and 3-D fluorescence analyses to investigate the impact of WSR at the Xiaolangdi (XLD) Reservoir on the sources and fluxes of dissolved organic carbon (DOC) and particulate organic carbon (POC) in the Yellow River. The POC and DOC fluxes during WSR (∼51 days) accounted for 95.5 % and 28.3 % of the annual fluxes. According to the Bayesian model used in the study, the fluxes of POC from sediment, terrestrial plants, and sewage increased by 23.2, 13.36, and 56.55 times, respectively, during the WSR period. On the other hand, the flux from various sources of DOC decreased by ∼0.7 times during the WSR process. The three-dimensional fluorescence index (specific UV absorbance [SUVA254], humification index [HIX], biological index [BIX], and fluorescence index [FI]) further reveals that in the WSR process, more DOC comes from sediment and upstream water. This study provides quantitative insights into the effects of WSR on river organic carbon export dynamics and the driving mechanisms behind them. It also has important implications for understanding the impact of anthropogenic disturbance on the global carbon cycle.

Pontiella agarivorans sp. nov., a novel marine anaerobic bacterium capable of degrading macroalgal polysaccharides and fixing nitrogen.

Marine macroalgae produce abundant and diverse polysaccharides, which contribute substantially to the organic matter exported to the deep ocean. Microbial degradation of these polysaccharides plays an important role in the turnover of macroalgal biomass. Various members of the Planctomycetes-Verrucomicrobia-Chlamydia (PVC) superphylum are degraders of polysaccharides in widespread anoxic environments. In this study, we isolated a novel anaerobic bacterial strain NLcol2T from microbial mats on the surface of marine sediments offshore Santa Barbara, CA, USA. Based on 16S ribosomal RNA (rRNA) gene and phylogenomic analyses, strain NLcol2T represents a novel species within the Pontiella genus in the Kiritimatiellota phylum (within the PVC superphylum). Strain NLcol2T is able to utilize various monosaccharides, disaccharides, and macroalgal polysaccharides such as agar and ɩ-carrageenan. A near-complete genome also revealed an extensive metabolic capacity for anaerobic degradation of sulfated polysaccharides, as evidenced by 202 carbohydrate-active enzymes (CAZymes) and 165 sulfatases. Additionally, its ability of nitrogen fixation was confirmed by nitrogenase activity detected during growth on nitrogen-free medium, and the presence of nitrogenases (nifDKH) encoded in the genome. Based on the physiological and genomic analyses, this strain represents a new species of bacteria that may play an important role in the degradation of macroalgal polysaccharides and with relevance to the biogeochemical cycling of carbon, sulfur, and nitrogen in marine environments. Strain NLcol2T (= DSM 113125T = MCCC 1K08672T) is proposed to be the type strain of a novel species in the Pontiella genus, and the name Pontiella agarivorans sp. nov. is proposed.IMPORTANCEGrowth and intentional burial of marine macroalgae is being considered as a carbon dioxide reduction strategy but elicits concerns as to the fate and impacts of this macroalgal carbon in the ocean. Diverse heterotrophic microbial communities in the ocean specialize in these complex polymers such as carrageenan and fucoidan, for example, members of the Kiritimatiellota phylum. However, only four type strains within the phylum have been cultivated and characterized to date, and there is limited knowledge about the metabolic capabilities and functional roles of related organisms in the environment. The new isolate strain NLcol2T expands the known substrate range of this phylum and further reveals the ability to fix nitrogen during anaerobic growth on macroalgal polysaccharides, thereby informing the issue of macroalgal carbon disposal.

Unveil of the role of fungal taxa in iron(III) reduction in paddy soil.

Hitherto, research on iron(III)-reduction has mainly focused on bacteria rather than fungal communities. To acquire insight into fungi involved in iron(III) reduction, typical organic matters (containing cellulose, glucose, lactate, and acetate) and ferrihydrite were used as electron donors and acceptors, respectively, in the presence of antibiotics. After antibiotic addition, microbial iron(III) reduction was still detected at quite high rates. In comparison, rates of iron(III) reduction were significantly lower in cellulose-amended groups than those with glucose, lactate, and acetate under the antibiotic-added condition. Patterns of intermediate (e.g., acetate, pyruvate, glucose) turnover were markedly different between treatments with and without antibiotics during organic degradation. A total of 20 genera of potential respiratory and fermentative iron(III)-reducing fungi were discovered based on ITS sequencing and genome annotation. This study provided an insight into the diversity of iron(III)-reducing fungi, indicating the underestimated contribution of fungi to iron and the coupled carbon biogeochemical cycling in environments.

Differential Adsorption of Dissolved Organic Matter and Phosphorus on Clay Mineral in Water-Sediment System.

Lake sediments connection to the biogeochemical cycling of phosphorus (P) and carbon (C) influences streamwater quality. However, it is unclear whether and how the type of sediment controls P and C cycling in water. Here, the adsorption behavior of montmorillonite (Mt) with different interlayer cations (Na+, Ca2+, or Fe3+) on dissolved organic matter (DOM) and P was investigated to understand the role of Mt in regulating the organic carbon-to-phosphate (OC/P) ratio within freshwater systems. The adsorption capacity of Fe-Mt for P was 3.2-fold higher than that of Ca-Mt, while it was 1/3 lower for DOM. This dissimilarity in adsorption led to an increased OC/P in Fe-Mt-dominated water and a decreased OC/P in Ca-Mt-dominated water. Moreover, an in situ atomic force microscope and high-resolution mass spectrometry revealed molecular fractionation mechanisms and adsorptive processes. It was observed that DOM inhibited the nucleation and crystallization processes of P on the Mt surface, and P affected the binding energy of DOM on Mt through competitive adsorption, thereby governing the interfacial P/DOM dynamics on Mt substrates at a molecular level. These findings have important implications for water quality management, by highlighting the role of clay minerals as nutrient sinks and providing new strategies for controlling P and C dynamics in freshwater systems.

A laser–laser method for carbonate C and O isotope measurement, metrology assessment, and stratigraphic applications

The stable isotopic compositions of carbon and oxygen (δ13Ccarb and δ18Ocarb) measured from carbonates are widely used in geology, notably to reconstruct paleotemperatures and the secular evolution of the biogeochemical carbon cycle, to characterize limestone sediment diagenesis, and to provide chemostratigraphy records. The standard technique used since the mid-20th century to measure C and O isotopic ratios is based on a wet chemical acid digestion protocol in order to evolve CO2 from carbonates—the latter being analyzed by mass spectrometry and, more recently, infrared spectroscopy. A newly developed laser-based method aims to circumvent this chemical preparation step by producing CO2 via an instant and spatially resolved calcination reaction. We describe an evolution of the laser calcination benchtop system previously described and used as a proof of concept toward a portable system, and we present the efficiency of this tool for performing carbon and oxygen isotope measurements from carbonate matrixes following standard evaluation metrology protocol. This metrological study explores the following: i) the use of internal standards; ii) inter-calibration with the traditional acid chemical preparation method; iii) analysis of the uncertainties of using GUM and ANOVA. Using 15 different types of carbonate minerals encompassing a range of isotopic VPDB compositions between −18.6‰ and +16.06‰ and between −14.80‰ and −1.72‰ for δ13Ccarb and δ18Ocarb, we show that isotopic cross-calibration is verified for both carbon and oxygen, respectively, and we demonstrate that the uncertainties (1σ) of the δ13Ccarb and δ18Ocarb measurements of laser–laser isotopic analysis are within 0.41‰ and 0.68‰, respectively. The advantages of this method in saving time and spatially resolved and automated analysis in situ are demonstrated by high-resolution chemostratigraphic analysis of a laminated lacustrine travertine sample.

Differentiation of prokaryotic community composition in suspended sediment size-fractionation in a small loess watershed

The transfer of particle-bound prokaryotes and substrates from slopes to rivers during soil erosion is a crucial dynamic process that greatly influences terrestrial biological and geochemical cycles. Particle size strongly affects the transport distance of suspended sediments and likely induces prokaryote and substrate variations along the course of the river. Previous studies have mainly focused on the spatial redistribution of soil prokaryotes, whereas the variation in prokaryotic diversity and community composition among different particle size-fractions in suspended sediments remain unclear. In this study, suspended sediments were collected at four plots (upstream, middle stream, downstream, and dam) along a river that runs through a valley. Sampled sediments were size-fractionated into > 63 μm and < 63 μm particles (referred to as small and large particle fractions hereafter), to identify the corresponding prokaryotic community composition, interactions, and functions. The richness index (Chao1 and observed species) and the diversity index (Shannon) of sediment-associated prokaryotic communities significantly decreased from upstream towards dam plots, except in the small particle fraction in downstream and dam plots. The highest β-diversity index value was found for the large particle fractions, while the geospatial contribution to β-diversity varied. The concentration of Proteobacteria in downstream (41.39 %) and dam (34.86 %) plots was lower than that in the upstream (47.65 %) and middle stream (45.90 %) plots. In contrast, Cyanobacteria (4.89 % and 6.75 %) and Verrucomicrobiota (5.98 % and 11.00 %) concentrations were greater in the downstream and dam plots, respectively, than those in the upstream (0.93 % and 2.43 %) and middle stream (3.37 % and 3.11 %) plots, respectively. Additionally, the concentrations of Verrucomicrobiota and Bacteroidota were significantly higher in the small particle fractions (2.26–8.12 % and 4.33–7.72 %) than those in the large particle fractions (2.03–5.94 % and 3.70–7.11 %). Compared to the other plots, upstream plots had a larger clustered network and a greater number of co-occurrences within the prokaryotic community in the bulk sediment and in the small particle fraction, whereas more complex interactions among prokaryotic communities were found in the large particle fraction from the dam plots. Soil organic carbon (SOC), total nitrogen (TN), and Olsen phosphorus were the three most influential factors, explaining 67.41 % of the variation in prokaryotic community. Proteobacteria and Myxococcota correlated negatively with SOC, TN, and Olsen P but positively with C = O. Conversely, Cyanobacteria and Verrucomicrobiota correlated positively with SOC, TN, and Olsen P but negatively with C = O. Functional groups linked to the biogeochemical cycling of carbon (methanol oxidation and methylotrophy) were found in high concentrations, whereas those linked to nitrogen (nitrogen and nitrate respiration) were found in low concentrations in upstream and middle stream plots. Reassembly of the sediment physicochemical characteristics among geospatial plots along the transport transect significantly altered the prokaryotic community composition and metabolic functional groups.

Precipitation fuels dissolved greenhouse gas (CO2, CH4, N2O) dynamics in a peatland-dominated headwater stream: results from a continuous monitoring setup

Stream ecosystems are actively involved in the biogeochemical cycling of carbon (C) and nitrogen (N) from terrestrial and aquatic sources. Streams hydrologically connected to peatland soils are suggested to receive significant quantities of particulate, dissolved, and gaseous C and N species, which directly enhance losses of greenhouse gases (GHGs), i.e., carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O), and fuel in-stream GHG production. However, riverine GHG concentrations and emissions are highly dynamic due to temporally and spatially variable hydrological, meteorological, and biogeochemical conditions. In this study, we present a complete GHG monitoring system in a peatland stream, which can continuously measure dissolved GHG concentrations and allows to infer gaseous fluxes between the stream and the atmosphere and discuss the results from March 31 to August 25 at variable hydrological conditions during a cool spring and warm summer period. Stream water was continuously pumped into a water-air equilibration chamber, with the equilibrated and actively dried gas phase being measured with two GHG analyzers for CO2 and N2O and CH4 based on Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS) and Non-Dispersive Infra-Red (NDIR) spectroscopy, respectively. GHG measurements were performed continuously with only shorter measurement interruptions, mostly following a regular maintenance program. The results showed strong dynamics of GHGs with hourly mean concentrations up to 9959.1, 1478.6, and 9.9 parts per million (ppm) and emissions up to 313.89, 1.17, and 0.40 mg C or N m−2h−1 for CO2, CH4, and N2O, respectively. Significantly higher GHG concentrations and emissions were observed shortly after intense precipitation events at increasing stream water levels, contributing 59% to the total GHG budget of 762.2 g m−2 CO2-equivalents (CO2-eq). The GHG data indicated a constantly strong terrestrial signal from peatland pore waters, with high concentrations of dissolved GHGs being flushed into the stream water after precipitation. During drier periods, CO2 and CH4 dynamics were strongly influenced by in-stream metabolism. Continuous and high-frequency GHG data are needed to assess short- and long-term dynamics in stream ecosystems and for improved source partitioning between in-situ and ex-situ production.

High niche specificity and host genetic diversity of groundwater viruses.

Viruses are key members of microbial communities that exert control over host abundance and metabolism, thereby influencing ecosystem processes and biogeochemical cycles. Aquifers are known to host taxonomically diverse microbial life, yet little is known about viruses infecting groundwater microbial communities. Here, we analysed 16 metagenomes from a broad range of groundwater physicochemistries. We recovered 1571 viral genomes that clustered into 468 high-quality viral operational taxonomic units. At least 15% were observed to be transcriptionally active, although lysis was likely constrained by the resource-limited groundwater environment. Most were unclassified (95%), and the remaining 5% were Caudoviricetes. Comparisons with viruses inhabiting other aquifers revealed no shared species, indicating substantial unexplored viral diversity. In silico predictions linked 22.4% of the viruses to microbial host populations, including to ultra-small prokaryotes, such as Patescibacteria and Nanoarchaeota. Many predicted hosts were associated with the biogeochemical cycling of carbon, nitrogen, and sulfur. Metabolic predictions revealed the presence of 205 putative auxiliary metabolic genes, involved in diverse processes associated with the utilization of the host's intracellular resources for biosynthesis and transformation reactions, including those involved in nucleotide sugar, glycan, cofactor, and vitamin metabolism. Viruses, prokaryotes overall, and predicted prokaryotic hosts exhibited narrow spatial distributions, and relative abundance correlations with the same groundwater parameters (e.g. dissolved oxygen, nitrate, and iron), consistent with host control over viral distributions. Results provide insights into underexplored groundwater viruses, and indicate the large extent to which viruses may manipulate microbial communities and biogeochemistry in the terrestrial subsurface.

Temperature, pH, and oxygen availability contributed to the functional differentiation of ancient Nitrososphaeria.

Ammonia-oxidizing Nitrososphaeria are among the most abundant archaea on Earth and have profound impacts on the biogeochemical cycles of carbon and nitrogen. In contrast to these well-studied ammonia-oxidizing archaea (AOA), deep-branching non-AOA within this class remain poorly characterized because of a low number of genome representatives. Here, we reconstructed 128 Nitrososphaeria metagenome-assembled genomes from acid mine drainage and hot spring sediment metagenomes. Comparative genomics revealed that extant non-AOA are functionally diverse, with capacity for carbon fixation, carbon monoxide oxidation, methanogenesis, and respiratory pathways including oxygen, nitrate, sulfur, or sulfate, as potential terminal electron acceptors. Despite their diverse anaerobic pathways, evolutionary history inference suggested that the common ancestor of Nitrososphaeria was likely an aerobic thermophile. We further surmise that the functional differentiation of Nitrososphaeria was primarily shaped by oxygen, pH, and temperature, with the acquisition of pathways for carbon, nitrogen, and sulfur metabolism. Our study provides a more holistic and less biased understanding of the diversity, ecology, and deep evolution of the globally abundant Nitrososphaeria.

Comparative single-cell genomics of Atribacterota JS1 in the Japan Trench hadal sedimentary biosphere.

Deep-sea and subseafloor sedimentary environments host heterotrophic microbial communities that contribute to Earth's carbon cycling. However, the potential metabolic functions of individual microorganisms and their biogeographical distributions in hadal ocean sediments remain largely unexplored. In this study, we conducted single-cell genome sequencing on sediment samples collected from six sites (7,445-8,023 m water depth) along an approximately 500 km transect of the Japan Trench during the International Ocean Discovery Program Expedition 386. A total of 1,886 single-cell amplified genomes (SAGs) were obtained, offering comprehensive genetic insights into sedimentary microbial communities in surface sediments (<1 m depth) above the sulfate-methane transition zone along the Japan Trench. Our genome data set included 269 SAGs from Atribacterota JS1, the predominant bacterial clade in these hadal environments. Phylogenetic analysis classified SAGs into nine distinct phylotypes, whereas metagenome-assembled genomes were categorized into only two phylotypes, advancing JS1 diversity coverage through a single cell-based approach. Comparative genomic analysis of JS1 lineages from different habitats revealed frequent detection of genes related to organic carbon utilization, such as extracellular enzymes like clostripain and α-amylase, and ABC transporters of oligopeptide from Japan Trench members. Furthermore, specific JS1 phylotypes exhibited a strong correlation with in situ methane concentrations and contained genes involved in glycine betaine metabolism. These findings suggest that the phylogenomically diverse and novel Atribacterota JS1 is widely distributed in Japan Trench sediment, playing crucial roles in carbon cycling within the hadal sedimentary biosphere.IMPORTANCEThe Japan Trench represents tectonically active hadal environments associated with Pacific plate subduction beneath the northeastern Japan arc. This study, for the first time, documented a large-scale single-cell and metagenomic survey along an approximately 500 km transect of the Japan Trench, obtaining high-quality genomic information on hadal sedimentary microbial communities. Single-cell genomics revealed the predominance of diverse JS1 lineages not recoverable through conventional metagenomic binning. Their metabolic potential includes genes related to the degradation of organic matter, which contributes to methanogenesis in the deeper layers. Our findings enhance understanding of sedimentary microbial communities at water depths exceeding 7,000 m and provide new insights into the ecological role of biogeochemical carbon cycling in the hadal sedimentary biosphere.

Reduced greenhouse gas emissions from particulate organic matter degradation in iron-enriched sediments.

Iron (Fe) plays an important role in the biogeochemical cycling of carbon and nutrients in aquatic systems. Reactive Fe phases can interact with organic carbon and facilitate the removal of carbon from the biogeochemical cycle; however, this important ecosystem function is often strongly controlled by Fe availability. Due to pollution from lignite mining in the Lusatian province in Northeast Germany, large amounts of iron and sulfate are released into the fluvial-lacustrine system of the Spree River. It was hypothesized that the input of freshly precipitated iron oxyhydroxides from mining areas (e.g., ferrihydrite) alter the biodegradation of particulate organic matter (POM) in downstream lacustrine sediments. To investigate the Fe-dependent degradation of POM, slurries mimicking iron-polluted sediments (85 mg Fe per g, 116 mg Fe per g, and 149 mg Fe per g dry weight) were incubated with plankton or leaf POM under anoxic and oxic headspace conditions, and CO2 and CH4 emissions, water chemistry, and stable isotopes of dissolved inorganic carbon were measured. The experiments revealed that (i) with an increasing Fe content, the CO2 and CH4 emissions were gradually reduced, (ii) CO2 and CH4 production was higher during plankton degradation than during leaf decomposition, and (iii) under oxic conditions, CO2 production was higher and CH4 production was lower when compared to the treatments under anoxic conditions. These findings demonstrate that while benthic mineralization of fresh POM typically releases greenhouse gases into the water column, the availability of iron oxyhydroxides can contribute to reduced greenhouse gas emissions from sediments. This is of considerable relevance for future carbon budgets of similar mining-affected, iron-polluted fluvial-lacustrine river systems.

Dissolved carbon dynamics and exchange in a high permeability beach aquifer

The biogeochemical transformation of dissolved carbon in tidal beaches affects the coastal carbon cycle and budget. Yet, the influence of groundwater flow on the behavior of dissolved carbon and CO2 flux across the different interfaces in these dynamic beach systems remains poorly understood, especially in deep beach aquifers. In this study, we investigated the biogeochemical reactions and origins of dissolved carbon and quantitatively evaluated CO2 outgassing driven by submarine groundwater discharge (SGD) in a high permeability beach aquifer (9–13 m depth) located in the South China Sea shelf. Results revealed that both dissolved inorganic carbon (DIC) and total alkalinity (TA) exhibited non-conservative additions across the salinity gradient. The excess DIC and TA most likely resulted from organic carbon decomposition in the brackish and saline zones. Aerobic respiration (upper saline plume zone), anaerobic reactions, and tidal mixing were identified as the dominant processes controlling DIC and TA dynamics. The mean CO2 outgassing flux across the beach sediment-air interface was estimated to be 1.05 g m−2 d−1, significantly higher than the CO2 flux across the sea-air interface. The outgassing pattern of groundwater CO2 from beach aquifer appeared to be driven by tidal pumping. Considering the combined effects of SGD-derived dissolved carbon and nutrients, we suggest that SGD yielded a net CO2 flux, contributing to 45 % of the CO2 flux across the sea-air interface. SGD directly and indirectly delivered substantial CO2 from the beach aquifer to the atmosphere, approximately (4.89–9.21) × 103 tons of CO2 per year along the 76.2 km long sandy coast. These findings demonstrate that intertidal beach aquifers, as active biogeochemical reactors have the strong potential to intensify CO2 emissions to the atmosphere through both beach sediment-air and sea-air interfaces. This study provides a better understanding of the links between carbon biogeochemical cycles and hydrologic processes in the coastal zones.

Effects of carbonate on ferrihydrite transformation in alkaline media.

Alkaline media widely exist in natural and engineered systems such as semiarid/arid areas, radioactive waste sites, and mine tailings. In these settings, the commonly occurring iron (oxyhydr)oxides differed in their ability to influence the fate of nutrients and contaminants. Due to the substantially increased atmospheric carbon dioxide (CO2) concentration, carbonate stands to increase in these media. However, how increasing carbonate affects the transformation of poorly crystalline iron (oxyhydr)oxides (e.g., two-line ferrihydrite) under alkaline conditions still remains unclear. Here, kinetics of ferrihydrite transformation were evaluated at pH ∼10 as a function of [carbonate] = 0-286 mM using synchrotron-based X-ray and vibrational spectroscopic techniques. The results showed that carbonate slowed down ferrihydrite transformation slightly and suppressed goethite formation, but promoted hematite formation regardless of its concentration. At low carbonate concentration (11.42 mM), the effect of carbonate on product formation was obvious due to the weak inner-sphere complex; however, at high carbonate concentration (80-286 mM), the effect was retarded because of the adsorption equilibrium of carbonate as well as the initial carbonate adsorption followed by desorption. Moreover, carbonate modified the morphology of hematite from rhombic to ellipsoidal to honeycomb and goethite from rod-like to needle-like to spindle-like due to the inner-sphere adsorption-desorption of carbonate and adsorption of hydroxyl ions on reactive sites of iron (oxyhydr)oxides in alkaline media. The results suggest that the concurrently increasing carbonate with enhanced atmospheric CO2 could control the transformation and occurrence of iron (oxyhydr)oxides in natural and engineered environments and have important implications for the biogeochemical cycles of iron and carbon.

Urbanization and weather dynamics co-dominated the spatial-temporal variation in pCO2 and CO2 fluxes in small montanic rivers draining diverse landscapes

Rivers have been widely reported as important CO2 emitters to the atmosphere. Rapid urbanization has a profound impact on the carbon biogeochemical cycle of rivers, leading to enhanced riverine CO2 evasions. However, it is still unclear whether the spatial–temporal patterns of CO2 emissions in the rivers draining diverse landscapes dominated by urbanization were stable, especially in mountainous areas. This study carried out a two-year investigation of water environmental hydrochemistry in three small mountainous rivers draining urban, suburban and rural landscapes in southwestern China, and CO2 partial pressure (pCO2) and fluxes (fCO2) in surface water were measured using headspace equilibrium method and classical thin boundary layer model. The average pCO2 and fCO2 in the highly urbanized river were of 4783.6 μatm and 700.0 mmol m−2 d−1, conspicuously higher than those in the rural river (1525.9 μatm and 123.2 mmol m−2 d−1), and the suburban river presented a moderate level (3114.2 μatm and 261.2 mmol m−2 d−1). It provided even clearer evidence that watershed urbanization could remarkably enhance riverine CO2 emissions. More importantly, the three rivers presented different longitudinal variations in pCO2, implying diversified spatial patterns of riverine CO2 emissions as a result of urbanization. The urban land can explain 49.6–69.1% of the total spatial variation in pCO2 at the reach scale, indicating that urban land distribution indirectly dominated the longitudinal pattern of riverine pCO2 and fCO2. pCO2 and fCO2 in the three rivers showed similar temporal variability with higher warm-rainy seasons and lower dry seasons, which are significantly controlled by weather dynamics, including monthly temperature and precipitation, but seem to be impervious to watershed urbanization. High temperature-stimulated microorganisms metabolism and riched-CO2 runoff input lead much higher pCO2 in warm-rainy seasons. However, it showed more sensitivity of pCO2 to monthly weather dynamics in urbanized rivers than that in rural rivers, and warm-rainy seasons showed hot moments of CO2 evasion for urban rivers. TOC, DOC, TN, pH and DO were the main controls on pCO2 in the urban and suburban rivers, while only pH and DO were connected with pCO2 in the rural rivers. This indicated differential controls and regulatory processes of pCO2 in the rivers draining diverse landscapes. Furthermore, it suggested that pCO2 calculated by the pH-total alkalinity method would obviously overestimate pCO2 in urban polluted rivers due to the inevitable influence of non-carbonate alkalinity, and thus, a relatively conservative headspace method should be recommended. We highlighted that urbanization and weather dynamics co-dominated the multiformity and uncertainty in spatial–temporal patterns of riverine CO2 evasions, which should be considered when modeling CO2 dynamics in urbanized rivers.

Spatiotemporal high-resolution mapping of biological production in the Southern Ocean

The Southern Ocean is considered to play an important role in the global biogeochemical cycles of carbon and nutrients. It is still unclear how biological production there impacts climate change owing to the remarkable gap between the current and the ideal state of research. Here, we proposed a new concept of combining Neural Network based parameterization of dissolved inorganic carbon with Biogeochemical Argo floats, showing simultaneously spatiotemporal distributions of net community production and resupply of carbon from the deep ocean based on the dissolved inorganic carbon change. It indicated a total net community production of 4.1 ± 0.3 Pg-C year−1 over the Southern Ocean, which accounts for 45% of global annual oceanic carbon export and is 20% higher than the previous estimates. Furthermore, net community production in the Southern Ocean has decreased by 0.8% year−1 since the 2010s, indicating that it may be contributing as positive feedback to global warming.

Unravelling molecular fractionation of dissolved organic matter on ferrihydrite-phosphate complexes

Association of dissolved organic matter (DOM) with iron (Fe) oxyhydroxides leading to significant molecular fractionation, plays a significant role in biogeochemical cycling of carbon in soils. However, the molecular effects of coexisting phosphate, a widely distributed oxyanion in agricultural soils that has a strong affinity with Fe oxyhydroxides on such a process remain poorly understood. Here, using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) with a superiority in deciphering DOM characteristics at the molecular level, this study reveals the DOM molecular fractionation characteristics on ferrihydrite-phosphate (Fh-P) complexes. Results show that the adsorption of DOM on Fh-P complexes can be significantly inhibited by ∼50% compared to that on ferrihydrite. Optical spectroscopy and FT-ICR-MS further indicate that phosphate can greatly change the molecular fractionation of DOM on Fh-P complexes. Phosphate preferentially inhibits the highly aromatic, hydrophobic, and high molecular weight compounds (> 400 Da) of DOM on Fh-P complexes, such as condensed hydrocarbon and tannin; more CHONS compounds preferentially adsorb on the Fh-P complexes than thoseon ferrihydrite. Phosphate inhibits the adsorption of DOM with the characteristics of high oxygen atoms number, aromaticity index (AI), and double bond equivalents (DBE) on ferrihydrite. Our study demonstrates that the inhibitory effects of phosphate on the adsorption of the DOM can significantly influence the fractionation and adsorption of DOM by ferrihydrite. The findings of this work deepen our understanding of biogeochemical cycling of DOM in soil and aquifer environments.

Instability in a carbon pool driven by multiple dissolved organic matter sources in a eutrophic lake basin: Potential factors for increased greenhouse gas emissions

Lakes serve as vital reservoirs of dissolved organic matter (DOM) and play pivotal roles in biogeochemical carbon cycles. However, the sources and compositions of DOM in freshwater lakes and their potential effects on lake sediment carbon pools remain unclear. In this study, seven inflowing rivers in the Lake Taihu basin were selected to explore the potential effects of multi-source DOM inputs on the stability of the lake sediment carbon pool. The results showed the high concentrations of dissolved organic carbon in the Lake Taihu basin, accompanied by a high complexity level. Lignins constituted the majority of DOM compounds, surpassing 40% of the total, while the organic carbon content was predominantly composed of humic acids (1.02–3.01 g kg−1). The high amounts of lignin oxidative cleavage led to CHO being the main molecular structure in the DOM of the seven rivers. The carbon constituents within the sediment carbon reservoir exhibited a positive correlation with dissolved CH4 and CO2, with a notable emphasis on humic acid and dissolved CH4 (R2 = 0.86). The elevated concentration of DOM, coupled with its intricate composition, contributed to the increases in dissolved greenhouse gases (GHGs). Experiments showed that the mixing of multi-source DOM can accelerate the organic carbon mineralization processes. The unit carbon emission efficiency was highest in the mixed group, reaching reached 160.9 μmol∙Cg−1, which also exhibited a significantly different carbon pool. The mixed decomposition of DOM from different sources influenced the roles of the lake carbon pool as source and sink, indicating that the multi-source DOM of this lake basin was a potential driving factor for increased carbon emissions. These findings have improved our understanding of the sources and compositions of DOM in lake basins and revealed their impacts on carbon emissions, thereby providing a theoretical basis for improving assessments of lake carbon emissions.

An intrusion and environmental effects of man-made silver nanoparticles in cold seeps

Silver nanoparticles (AgNPs) are among the most widely used metal-based engineered nanomaterials in biomedicine and nanotechnology, and account for >50 % of global nanomaterial consumer products. The increasing use of AgNPs potentially causes marine ecosystem changes; however, the environmental impacts of man-made AgNPs are still poorly studied. This study reports for the first time that man-made AgNPs intruded into cold seeps, which are important marine ecosystems where hydrogen sulfide, methane, and other hydrocarbon-rich fluid seepage occur. Using a combination of electron microscopy, geochemical and metagenomic analyses, we found that in the cold seeps with high AgNPs concentrations, the relative abundance of genes associated with anaerobic oxidation of methane (AOM) was lower, while those related to the sulfide oxidizing and sulfate reducing were higher. This suggests that AgNPs can stimulate the proliferation of sulfate-reducing and sulfide-oxidizing bacteria, likely due to the effects of activating repair mechanisms of the cells against the toxicant. A reaction of AgNPs with hydrogen sulfide to form silver sulfide could also effectively reduce the amount of available sulfate in local ecosystems, which is generally used as the AOM oxidant. These novel findings indicate that man-made AgNPs may be involved in the biogeochemical cycles of sulfur and carbon in nature, and their potential effects on the releasing of methane from the marine methane seeps should not be ignored in both scientific and environmental aspects.

Higher temperature, increased CO2, and changing nutrient ratios alter the carbon metabolism and induce oxidative stress in a cosmopolitan diatom

AbstractPhytoplankton are responsible for about 90% of the oceanic primary production, largely supporting marine food webs, and actively contributing to the biogeochemical cycling of carbon. Yet, increasing temperature and pCO2, along with higher dissolved nitrogen: phosphorus ratios in coastal waters are likely to impact phytoplankton physiology, especially in terms of photosynthetic rate, respiration, and dissolved organic carbon (DOC) production. Here, we conducted a full‐factorial experiment to identify the individual and combined effects of temperature, pCO2, and N : P ratio on the antioxidant capacity and carbon metabolism of the diatom Phaeodactylum tricornutum. Our results demonstrate that, among these three drivers, temperature is the most influential factor on the physiology of this species, with warming causing oxidative stress and lower activity of antioxidant enzymes. Furthermore, the photosynthetic rate was higher under warmer conditions and higher pCO2, and, together with a lower dark respiration rate and higher DOC exudation, generated cells with lower carbon content. An enhanced oceanic CO2 uptake and an overall stimulated microbial loop benefiting from higher DOC exudation are potential longer‐term consequences of rising temperatures, elevated pCO2 as well as shifted dissolved N : P ratios.