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Nitrous oxide (N2O) is a strong greenhouse gas and stratospheric ozone-depleting substance. Around 20% of global emissions stem from the ocean, but current estimates and future projections are uncertain due to poor spatial coverage over large areas and limited understanding of drivers of N2O dynamics. Here, we focus on the extensive and particularly data-lean Arctic Ocean shelves north of Siberia that experience rapid warming and increasing input of land-derived nitrogen with permafrost thaw. We combine water column N2O measurements from two expeditions with on-board incubation of intact sediment cores to assess N2O dynamics and the impact of land-derived nitrogen. Elevated nitrogen concentrations in water column and sediments were observed near large river mouths. Concentrations of N2O were only weakly correlated with dissolved nitrogen and turbidity, reflecting particulate matter from rivers and coastal erosion, and correlations varied between river plumes. Surface water N2O concentrations were on average close to equilibrium with the atmosphere, but varied widely (N2O saturation 38%-180%), indicating strong local N2O sources and sinks. Water column N2O profiles and low sediment-water N2O fluxes do not support strong sedimentary sources or sinks. We suggest that N2O dynamics in the region are influenced by water column N2O consumption under aerobic conditions or in anoxic microsites of particles, and possibly also by water column N2O production. Changes in biogeochemical and physical conditions will likely alter N2O dynamics in the Siberian Arctic Ocean over the coming decades, in addition to reduced N2O solubility in a warmer ocean.

Effects of aerosols such as black carbon (BC) on climate and buildup of the monsoon over the Indian Ocean are insufficiently quantified. Uncertain contributions from various natural and anthropogenic sources impede our understanding. Here, we use observations over 5 y of BC and its isotopes at a remote island observatory in northern Indian Ocean to constrain loadings and sources during little-studied monsoon season. Carbon-14 data show a highly variable yet largely fossil (65 ± 15%) source mixture. Combining carbon-14 with carbon-13 reveals the impact of African savanna burning, which occasionally approach 50% (48 ± 9%) of the total BC loadings. The BC mass-absorption cross-section for this regime is 7.6 ± 2.6 m2/g, with higher values during savanna fire input. Taken together, the combustion sources, longevity, and optical properties of BC aerosols over summertime Indian Ocean are different than the more-studied winter aerosol, with implications for chemical transport and climate model simulations of the Indian monsoon.

Black carbon (BC) aerosols perturb climate and impoverish air quality/ human health-affecting similar to 1.5 billion people in South Asia. However, the lack of source-diagnostic observations of BC is hindering the evaluation of uncertain bottom-up emission inventories (EIs) and thereby also models/policies. Here, we present dual-isotope-based (Delta C-14/delta C-13) fingerprinting of wintertime BC at two receptor sites of the continental outflow. Our results show a remarkable similarity in contributions of biomass and fossil combustion, both from the site capturing the highly populated highly polluted Indo-Gangetic Plain footprint (IGP; Delta C-14-f(biomass) = 50 +/- 3%) and the second site in the N. Indian Ocean representing a wider South Asian footprint (52 +/- 6%). Yet, both sites reflect distinct delta C-13-fingerprints, indicating a distinguishable contribution of C-4-biomass burning from peninsular India (PI). Tailored-model-predicted seasonaveraged BC concentrations (700 +/- 440 ng m(-3)) match observations (740 +/- 250 ng m(-3)), however, unveiling a systematically increasing model-observation bias (+19% to -53%) through winter. Inclusion of BC from open burning alone does not reconcile predictions (f(biomass) = 44 +/- 8%) with observations. Direct source-segregated comparison reveals regional offsets in anthropogenic emission fluxes in EIs, overestimated fossil-BC in the IGP, and underestimated biomass-BC in PI, which contributes to the model-observation bias. This ground-truthing pinpoints uncertainties in BC emission sources, which benefit both climate/air-quality modeling and mitigation policies in South Asia.

Black carbon (BC) aerosols affect climate, especially in high aerosol loading regions such as South Asia. A key uncertainty for the climate effects of BC is the evolution of light-absorbing properties in the atmosphere. Here, we present a year-round comparison of the mass absorption cross section (MAC; 678 nm) of BC in air (PM10) and rain, for samples collected at the Maldives Climate Observatory at Hanimaadhoo. We develop a filter-loading correction scheme for estimating BC absorption on filters used in high-volume samplers. The year-round average MAC(678) of BC in the rain is almost twice (13.3 +/- 4.2 m(2)/g) compared to the PM10 aerosol (7.2 +/- 2.6 m(2)/g). A possible explanation is the elevated ratio of organic carbon (OC) to BC observed in rain particulate matter (9.4 +/- 6.3) compared to in the aerosols (OC/BC 2.6 +/- 1.4 and water-insoluble organic carbon/BC 1.2 +/- 0.8), indicating a coating-enhancement effect. In addition to BC, we also investigated the MAC(365) of water-soluble brown carbon in PM10 (0.4 +/- 0.4 m(2)/g, at 365 nm). In contrast to BC, MAC(365)brown carbon relates to air mass history, showing higher values for samples from air originating over the South Asian landmass. Furthermore, calculated washout ratios are much lower for BC compared to OC and inorganic ions such as sulfate, implying a longer atmospheric lifetime for BC. The wet deposition flux for BC during the high loading winter was 3 times higher than during the wet summer, despite much less precipitation in the winter.

According to ecological theory, two species cannot occupy the same niche. Using nitrogen isotope analyses (delta N-15) of amino acids, we tested the extent to which two sympatric deposit-feeding amphipods,Monoporeia affinisandPontoporeia femorata, partition their trophic resources. We found that trophic position (TP) and resynthesis index ( n-ary sumation V; a proxy for degradation status of ingested material prior to assimilation by the consumer) differ between species. The surface-feedingM. affinishad higher TP and intermediate n-ary sumation V, both pointing to a large contribution of metazoans in its diet.P. femorata, which feeds in the subsurface layers, had lower TP and a bimodal distribution of the n-ary sumation V values, supporting previous experimental evidence of a larger feeding niche. We also evaluated whether TP and n-ary sumation V values have consequences for amphipod fecundity and embryo viability and found that embryo viability inM. affiniswas negatively linked to TP. Our results indicate that the amino acid-delta N-15 data paired with information about reproductive status are useful for detecting differences in the trophic ecology of sympatric amphipods.

Black carbon (BC) contributes to Arctic climate warming, yet source attributions are inaccurate due to lacking observational constraints and uncertainties in emission inventories. Year-round, isotope-constrained observations reveal strong seasonal variations in BC sources with a consistent and synchronous pattern at all Arctic sites. These sources were dominated by emissions from fossil fuel combustion in the winter and by biomass burning in the summer. The annual mean source of BC to the circum-Arctic was 39 +/- 10% from biomass burning. Comparison of transport-model predictions with the observations showed good agreement for BC concentrations, with larger discrepancies for (fossil/biomass burning) sources. The accuracy of simulated BC concentration, but not of origin, points to misallocations of emissions in the emission inventories. The consistency in seasonal source contributions of BC throughout the Arctic provides strong justification for targeted emission reductions to limit the impact of BC on climate warming in the Arctic and beyond.

Stable nitrogen isotopes (delta N-15) are used as indicators of trophic position (TP) of consumers. Deriving TP from delta N-15 of individual amino acids (AAs) is becoming popular in ecological studies, because of lower uncertainty than TP based on bulk delta N-15 (TPbulk). This method would also facilitate biomagnification studies provided that isotope fractionation is unaffected by toxic exposure. We compared TPAA and TPbulk estimates for a sediment-dwelling bivalve from two coastal sites, a pristine and a contaminated. Chemical analysis of PCB levels in mussels, sediments, and pore water confirmed the expected difference between sites. Both methods, but in particular the TPAA underestimated the actual TP of bivalves. Using error propagation, the total uncertainty related to the analytical precision and assumptions in the TP calculations was found to be similar between the two methods. Interestingly, the significantly higher intercept for the regression between T-AA, and TPbulk in the contaminated site compared to the pristine site indicates a higher deamination rate due to detoxification as a result of chronic exposure and a higher N-15 fractionation. Hence, there is a need for controlled experiments on assumptions underlying amino acid-specific stable isotope methods in food web and bimagnification studies.

Methyl chloride and methyl bromide (CH3Cl and CH3Br) are the largest natural sources of chlorine and bromine, respectively, to the stratosphere, where they contribute to ozone depletion. We report the anthropogenic production of CH3Cl and CH3Br during breadbaking, and suggest this production is an abiotic process involving the methyl ester functional groups in pectin and lignin structural polymers of plant cells. Wide variations in baking styles allow only rough estimates of this flux of methyl halides on a global basis. A simple model suggests that CH3Br emissions from breadbaking likely peaked circa 1990 at approximately 200 tonnes per year (about 0.3% of industrial production), prior to restrictions on the dough conditioner potassium bromate. In contrast, CH3Cl emissions from breadbaking may be of similar magnitude as acknowledged present-day CH3Cl industrial emissions. Because the mechanisms involve functional groups and compounds widely found in plant materials, this type of methyl halide production may occur in other cooking techniques as well.

RationaleThe environmental occurrence of chlorinated acetic acids (CAAs) has been extensively studied, but the sources and transport are still not yet fully understood. A promising approach for source apportionment and process studies is the isotopic characterization of target compounds. We present the first on-line stable chlorine isotope analysis of CAAs by use of gas chromatography/quadrupole mass spectrometry (GC/qMS). MethodsFollowing approved procedures for concentration analysis, CAAs extracted into MTBE were methylated to GC-amenable methyl esters (mCAAs). These mCAAs were then analyzed by GC/qMS for their stable chlorine isotope composition using a sample/standard-bracketing approach (CAA standards in the range Cl-37 -6.3 to -0.2 , Standard Mean Ocean Chloride). ResultsCross-calibration of the herein presented method with off-line reference methods (thermal ionization and continuous-flow GC isotope ratio mass spectrometry; TI-MS and CF-GC/IRMS, respectively) shows good agreement between the methods (regression slope for GC/qMS vs reference method data sets: 0.92 +/- 0.29). Sample amounts as small as 10 pmol Cl can herewith be analyzed with a precision of 0.1 to 0.4 parts per thousand. ConclusionsThis method should be useful for environmental studies of CAAs at ambient concentrations in precipitations (<0.06 to 100nmolL(-1)), surface waters (<0.2 to 5nmolL(-1)) and soil (<0.6 to 2000nmolkg(-1) dry soil) where conventional off-line methods cannot be applied.

info:eu-repo/semantics/published

info:eu-repo/semantics/published

The widespread use of chlorinated phenols (CPs) as a wood preservative has led to numerous contaminated sawmill sites. However, it remains challenging to assess the extent of in situ degradation of CPs. We evaluated the use of compound-specific chlorine and carbon isotope analysis (Cl- and C-CSIA) to assess CP biotransformation. In a laboratory system, we measured isotopic fractionation during oxidative 2,4,6-trichlorophenol dechlorination by representative soil enzymes (C. fumago chloroperoxidase, horseradish peroxidase, and laccase from T. versicolor). Using a mathematical model, the validity of the Rayleigh approach to evaluate apparent kinetic isotope effects (AKIE) was confirmed. A small but significant Cl-AKIE of 1.0022 ± 0.0006 was observed for all three enzymes, consistent with a reaction pathway via a cationic radical species. For carbon, a slight inverse isotope effect was observed (C-AKIE = 0.9945 ± 0.0019). This fractionation behavior is clearly distinguishable from reported reductive dechlorination mechanisms. Based on these results we then assessed degradation and apportioned different types of technical CP mixtures used at two former sawmill sites. To our knowledge, this is the first study that makes use of two-element CSIA to study sources and transformation of CPs in the environment.