Evidence for anthropogenic ¹⁴C-enrichment in estuarine waters adjacent to the North Sea

[1] The isotopic composition (d13C and D14C) of high molecular weight dissolved organic carbon (HMW DOC) was studied in the Tyne and Tweed estuaries, NE England. Despite significant removal of terrigenous HMW DOC in the low salinity regions (S < 15), D14C remained modern with little variation around 115%. This lack of apparent age discrimination was attributed to either non-oxidative removal or the absence of a significant proportion of old refractory C in the HMW DOC pool. At S < 15, we observed seaward increases in d13C and D14C. With no documented local 14C inputs, we attributed non-bomb related 14C-enrichment at S < 15 to a possible ‘lingering effect’ of distal anthropogenic sources in near-coastal North Sea HMW DOC. Given the global distribution of potential sources, we propose that anthropogenic 14C should be considered in assigning ages of DOC pools in near-coastal waters and suggest its possible use as a tracer for DOC transformations

Variability in aerobic methane oxidation over the past 1.2 Myrs recorded in microbial biomarker signatures from Congo fan sediments

Methane (CH4) is a strong greenhouse gas known to have perturbed global climate in the past, especially when released in large quantities over short time periods from continental or marine sources. It is therefore crucial to understand and, if possible, quantify the individual and combined response of these variable methane sources to natural climate variability. However, past changes in the stability of greenhouse gas reservoirs remain uncertain and poorly constrained by geological evidence. Here, we present a record from the Congo fan of a highly specific bacteriohopanepolyol (BHP) biomarker for aerobic methane oxidation (AMO), 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), that identifies discrete periods of increased AMO as far back as 1.2 Ma. Fluctuations in the concentration of aminopentol, and other 35-aminoBHPs, follow a pattern that correlates with late Quaternary glacial-interglacial climate cycles, with highest concentrations during warm periods. We discuss possible sources of aminopentol, and the methane consumed by the precursor methanotrophs, within the context of the Congo River setting, including supply of methane oxidation markers from terrestrial watersheds and/or marine sources (gas hydrate and/or deep subsurface gas reservoir). Compound-specific carbon isotope values of −30‰ to −40‰ for BHPs in ODP 1075 and strong similarities between the BHP signature of the core and surface sediments from the Congo estuary and floodplain wetlands from the interior of the Congo River Basin, support a methanotrophic and likely terrigenous origin of the 35-aminoBHPs found in the fan sediments. This new evidence supports a causal connection between marine sediment BHP records of tropical deep sea fans and wetland settings in the feeding river catchments, and thus tropical continental hydrology. Further research is needed to better constrain the different sources and pathways of methane emission. However, this study identifies the large potential of aminoBHPs, in particular aminopentol, to trace and, once better calibrated and understood, quantify past methane sources and fluxes from terrestrial and potentially also marine sources

Biomass offsets little or none of permafrost carbon release from soils, streams, and wildfire: an expert assessment

As the permafrost region warms, its large organic carbon pool will be increasingly vulnerable to decomposition, combustion, and hydrologic export. Models predict that some portion of this release will be offset by increased production of Arctic and boreal biomass; however, the lack of robust estimates of net carbon balance increases the risk of further overshooting international emissions targets. Precise empirical or model-based assessments of the critical factors driving carbon balance are unlikely in the near future, so to address this gap, we present estimates from 98 permafrost-region experts of the response of biomass, wildfire, and hydrologic carbon flux to climate change. Results suggest that contrary to model projections, total permafrost-region biomass could decrease due to water stress and disturbance, factors that are not adequately incorporated in current models. Assessments indicate that end-of-the-century organic carbon release from Arctic rivers and collapsing coastlines could increase by 75% while carbon loss via burning could increase four-fold. Experts identified water balance, shifts in vegetation community, and permafrost degradation as the key sources of uncertainty in predicting future system response. In combination with previous findings, results suggest the permafrost region will become a carbon source to the atmosphere by 2100 regardless of warming scenario but that 65%–85% of permafrost carbon release can still be avoided if human emissions are actively reduced

Organic matter sources, fluxes and greenhouse gas exchange in the Oubangui River (Congo River basin)

The Oubangui is a major tributary of the Congo River, draining an area of 500 000 km2 mainly consisting of wooded savannahs. Here, we report results of a one year long, 2-weekly sampling campaign in Bangui (Central African Republic) since March 2010 for a suite of physicochemical and biogeochemical characteristics, including total suspended matter (TSM), bulk concentration and stable isotope composition of particulate organic carbon (POC and 13CPOC), particulate nitrogen (PN and 15NPN), dissolved organic carbon (DOC and 13CDOC), dissolved inorganic carbon (DIC and 13CDIC), dissolved greenhouse gases (CO2, CH4 and N2O), and dissolved ignin composition. 13C signatures of both POC and DOC showed strong seasonal variations −30.6 to −25.8 ‰, and −31.8 to −27.1 ‰, respectively), but their different timing indicates that the origins of POC and DOC may vary strongly over the hydrograph and are largely ncoupled, differing up to 6‰ in 13C signatures. Dissolved lignin characteristics (carbon- ormalised yields, cinnamyl:vanillyl phenol ratios, and vanillic acid to vanillin ratios) showed arked differences between high and low discharge conditions, consistent with major seasonal ariations in the sources of dissolved organic matter. We observed a strong seasonality in pCO2, ranging between 470 ± 203 ppm for Q<1000m3 s−1 (n = 10) to a maximum of 3750 pm during the first stage of the rising discharge. The low POC/PN ratios, high %POCand low and variable 13CPOC signatures during low flow conditions suggest that the majority of the POC pool during this period consists of in situ produced phytoplankton, consistent with oncurrent pCO2 (partial pressure of CO2) values only slightly above and, occasionally, below atmospheric equilibrium. Water-atmosphere CO2 fluxes estimated using two independent pproaches averaged 105 and 204 gCm−2 yr−1, i.e. more than an order of magnitude lower than current estimates for large tropical rivers globally. Although tropical rivers are often ssumed to show much higher CO2 effluxes compared to temperate systems, we show that in situ production may be high enough to dominate the particulate organic carbon pool, and lower CO2 values to near equilibrium values during low discharge conditions. The total annual flux of TSM, POC, PN, DOC and DIC are 2.33 Tg yr−1, 0.14 TgC yr−1, 0.014 TgNyr−1, 0.70 TgC yr−1, and 0.49 Tg Cyr−1, respectively. While our TSM and POC fluxes are similar to previous stimates for the Oubangui, DOC fluxes were 30% higher and bicarbonate fluxes were 35% ower than previous reports. DIC represented 58% of the total annual C flux, and under the ssumptions that carbonate weathering represents 25% of the DIC flux and that CO2 from espiration drives chemical weathering, this flux is equivalent to 50% of terrestrial-derived riverine C transport.AFRIVA

Bacteriohopanepolyols in tropical soils and sediments from the Congo River catchment area

The Congo River basin drains the second largest area of tropical rainforest in the world, including a large proportion of pristine wetlands. We present the bacteriohopanepolyol (BHP) inventory of a suite of tropical soils and, from comparison with published data, propose some initial ideas on BHP distribution controls. Strong taxonomic controls on BHP production are evident in wetland sediments. Dominant within the suite were 35-aminobacteriohopane-31,32,33,34-tetrol (aminotetrol) and 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), indicating aerobic methanotrophy. A narrow range and low mean relative abundance of 30-(5′-adenosyl)hopane (adenosylhopane) and related compounds, collectively termed “soil marker” BHPs, were observed in Congo soils (mean 17%, range 7.9–36% of total BHPs, n = 22) compared with literature data from temperate surface soils and Arctic surface soils (mean 36%, range 0–66% of total BHPs, n = 28) suggesting a greater rate of conversion of these BHP precursors to other structures

Improving water quality in China: environmental investment pays dividends

This study highlights how Chinese economic development detrimentally impacted water quality in recent decades and how this has been improved by enormous investment in environmental remediation funded by the Chinese government. To our knowledge, this study is the first to describe the variability of surface water quality in inland waters in China, the affecting drivers behind the changes, and how the government-financed conservation actions have impacted water quality. Water quality was found to be poorest in the North and the Northeast China Plain where there is greater coverage of developed land (cities + cropland), a higher gross domestic product (GDP), and higher population density. There are significant positive relationships between the concentration of the annual mean chemical oxygen demand (COD) and the percentage of developed land use (cities + cropland), GDP, and population density in the individual watersheds (p < 0.001). During the past decade, following Chinese government-financed investments in environmental restoration and reforestation, the water quality of Chinese inland waters has improved markedly, which is particularly evident from the significant and exponentially decreasing GDP-normalized COD and ammonium (NH4+-N) concentrations. It is evident that the increasing GDP in China over the past decade did not occur at the continued expense of its inland water ecosystems. This offers hope for the future, also for other industrializing countries, that with appropriate environmental investments a high GDP can be reached and maintained, while simultaneously preserving inland aquatic ecosystems, particularly through management of sewage discharge.Yongqiang Zhou, Jianrong Mad, Yunlin Zhang, Boqiang Qin, Erik Jeppesen ... Justin D.Brookes ... et al

Dissolved organic carbon loss from Yedoma permafrost amplified by ice wedge thaw

Pleistocene Yedoma permafrost contains nearly a third of all organic matter (OM) stored in circum-arctic permafrost and is characterized by the presence of massive ice wedges. Due to its rapid formation by sediment accumulation and subsequent frozen storage, Yedoma OM is relatively well preserved and highly biologically available (biolabile) upon thaw. A better understanding of the processes regulating Yedoma degradation is important to improve estimates of the response and magnitude of permafrost carbon feedbacks to climate warming. In this study, we examine the composition of ice wedges and the influence of ice wedge thaw on the biolability of Yedoma OM. Incubation assays were used to assess OM biolability, fluorescence spectroscopy to characterize the OM composition, and potential enzyme activity rates to examine the controls and regulation of OM degradation.We show that increasing amounts of ice wedge melt water in Yedoma-leached incubations enhanced the loss of dissolved OM over time. This may be attributed to the presence of low-molecular weight compounds and low initial phenolic content in the OM of ice wedges, providing a readily available substrate that promotes the degradation of Yedoma OC. The physical vulnerability of ice wedges upon thaw (causing irreversible collapse), combined with the composition of ice wedge-engrained OM (co-metabolizing old OM), underlines the particularly strong potential of Yedoma to generate a positive feedback to climate warming relative to other forms of non-ice wedge permafrost

An initial investigation into the organic matter biogeochemistry of the Congo River

The Congo River, which drains pristine tropical forest and savannah and is the second largest exporter of terrestrial carbon to the ocean, was sampled in early 2008 to investigate organic matter (OM) dynamics in this historically understudied river basin. We examined the elemental (%OC, %N, C:N), isotopic (δ13C, Δ14C, δ15N) and biochemical composition (lignin phenols) of coarse particulate (&#62;63 μm; CPOM) and fine particulate (0.7–63 μm; FPOM) OM and DOC, δ13C, Δ14C and lignin phenol composition with respect to dissolved OM (&#60;0.7 μm; DOM) from five sites in the Congo River Basin. At all sample locations the organic carbon load was dominated by the dissolved phase (∼82–89% of total organic carbon) and the total suspended sediment load was principally fine particulate material (∼81–91% fine suspended sediment). Distinct compositional and isotopic differences were observed between all fractions. Congo CPOM, FPOM and DOM all originated from vegetation and soil inputs as evidenced by elemental, isotopic and lignin phenol data, however FPOM was derived from much older carbon pools (mean Δ14C = −62.2 ± −13.2‰, n = 5) compared to CPOM and DOM (mean Δ14C = 55.7 ± 30.6‰, n = 4 and 73.4 ± 16.1‰, n = 5 respectively). The modern radiocarbon ages for DOM belie a degraded lignin compositional signature (i.e. elevated acid:aldehyde ratios (Ad:Al) relative to CPOM and FPOM), and indicate that the application of OM degradation patterns derived from particulate phase studies to dissolved samples needs to be reassessed: these elevated ratios are likely attributable to fractionation processes during solubilization of plant material. The relatively low DOM carbon-normalized lignin yields (Λ8; 0.67–1.12 (mg(100 mg OC)−1)) could also reflect fractionation processes, however, they have also been interpreted as an indication of significant microbial or algal sources of DOM. CPOM appears to be well preserved higher vascular plant material as evidenced by its modern radiocarbon age, elevated C:N (17.2–27.1) and Λ8 values (4.56–7.59 (mg(100 mg OC)−1)). In relation to CPOM, the aged FPOM fraction (320–580 ybp 14C ages) was comparatively degraded, as demonstrated by its nitrogen enrichment (C:N 11.4–14.3), lower Λ8 (2.80–4.31 (mg(100 mg OC)−1)) and elevated lignin Ad:Al values similar to soil derived OM. In this study we observed little modification of the OM signature from sample sites near the cities of Brazzaville and Kinshasa to the head of the estuary (∼350 km) highlighting the potential for future studies to assess seasonal and long-term OM dynamics from this logistically feasible location and derive relevant information with respect to OM exported to the Atlantic Ocean. The relative lack of OM data for the Congo River Basin highlights the importance of studies such as this for establishing baselines upon which to gauge future change