Coking is a substantial source of carbonaceous aerosols in China, but the emission characteristics and pollution levels of coking-produced organic carbon (OC) and elemental carbon (EC) remain unknown, causing considerable uncertainty in emission estimates. In this study, the emission factors of OC (EFOC) and EC (EFEC) of typical coking plants in Shanxi, China, were measured. The measured EFEC and EFOC from fugitive emissions (7.43 and 9.54 g/t) were significantly higher than those from flue gas (1.67 and 3.71 g/t). The technological conditions of coke production affect the emissions of OC and EC. For example, the total emissions from coke plants that use 3.2-m-high coke ovens were greater than those from plants that use 4.3- and 6-m-high ovens. The EFOC and EFEC for plants conducting stamp charging were considerably higher than those for plants using top charging. The stable carbon isotopes of total carbon (δ¹³CTC), OC (δ¹³COC), and EC (δ¹³CEC) for fly ash during coking were −23.74‰ to −24.17‰, −23.32‰ to −23.87‰, and −23.84‰ to −24.14‰, respectively, and no clear isotopic fractionation was found during coke production. Different EC/OC ratios from different emission pathways and the carbon isotope signature of coke production should be considered when investigating the sources of carbonaceous aerosols. The total estimated EC and OC emissions from coke production in China were 3.93 and 5.72 Gg in 2017, and Shanxi, Hebei, and Shaanxi made the largest contributions.

The determination of both stable nitrogen (δ¹⁵N–NO₃⁻) and stable oxygen (δ¹⁸O–NO₃⁻) isotopic signatures of nitrate in PM₂.₅ has shown potential for an approach of assessing the sources and oxidation pathways of atmospheric NOx (NO+NO₂). In the present study, daily PM₂.₅ samples were collected in the megacity of Beijing, China during the winter of 2017–2018, and this new approach was used to reveal the origin and oxidation pathways of atmospheric NOx. Specifically, the potential of field δ¹⁵N–NO₃⁻ signatures for determining the NOx oxidation chemistry was explored. Positive correlations between δ¹⁸O–NO₃⁻ and δ¹⁵N–NO₃⁻ were observed (with R² between 0.51 and 0.66, p < 0.01), and the underlying environmental significance was discussed. The results showed that the pathway-specific contributions to NO₃⁻ formation were approximately 45.3% from the OH pathway, 46.5% from N₂O₅ hydrolysis, and 8.2% from the NO₃+HC channel based on the δ¹⁸O-δ¹⁵N space of NO₃⁻. The overall nitrogen isotopic fractionation factor (εN) from NOx to NO₃⁻ on a daily scale, under winter conditions, was approximately +16.1‰±1.8‰ (consistent with previous reports). Two independent approaches were used to simulate the daily and monthly ambient NOx mixtures (δ¹⁵N-NOx), respectively. Results indicated that the monthly mean values of δ¹⁵N-NOx compared well based on the two approaches, with values of −5.5‰ ± 2.6‰, −2.7‰ ± 1.9‰, and −3.2‰ ± 2.2‰ for November, December, and January (2017–2018), respectively. The uncertainty was in the order of 5%, 5‰ and 5.2‰ for the pathway-specific contributions, the εN, and δ¹⁵N-NOx, respectively. Results also indicated that vehicular exhaust was the key contributor to the wintertime atmospheric NOx in Beijing (2017–2018). Our advanced isotopic perspective will support the future assessment of the origin and oxidation of urban atmospheric NOx.

The installation rate of denitrification devices is accelerating in Chinese urban boilers. Previous studies on pulverized coal-fired boilers without denitrification devices showed that combustion products containing mainly oxidized mercury (Hg) preferably enriched lighter Hg isotopes than feed coals. However, the magnitude of this enrichment becomes less pronounced if denitrification devices are installed. The underlying Hg isotope fractionation mechanisms are still unclear. In this study, three types of urban boilers (two pulverized coal-fired boilers, one circulating fluidized bed boiler and one municipal waste incinerator boiler) all installed with denitrification devices were measured for Hg isotope compositions of their feed fuels and corresponding combustion products. We observed little mass independent fractionation but very significant mass dependent fractionation (MDF) between feed fuels and combustion products. The fly ash and desulfurization products both enriched heavier Hg isotopes than feed coals in three coal-fired boilers, and the enrichment of heavy Hg isotopes increased with sequential removal of combustion products in all boilers. Different from previously suggested kinetic MDF for gaseous Hg⁰(g)→Hgᴵᴵ(g) and gaseous Hgᴵᴵ(g)→particulate Hgᴵᴵ(p) in coal combustion flue gases, we propose an equilibrium MDF for Hg⁰(g)↔Hgᴵᴵ(g) followed by a kinetic MDF for Hgᴵᴵ(g)→Hgᴵᴵ(p). This equilibrium MDF most likely occurs during Hg⁰(g) oxidation in denitrification devices, which enriches heavy Hg isotopes in oxidized products (Hgᴵᴵ(g) and Hgᴵᴵ(p)) that are then sequestrated in fly ash and desulfurization products. The paradigm shift of MDF in boilers with denitrification devices was further verified by parallel Hg isotope measurement in urban atmosphere particulates. Our study clearly demonstrates that modern coal-fired boilers with denitrification devices have a quite different MDF compared to traditional boilers without denitrification devices. This has important implications for estimating isotope signatures of urban boiler Hg emissions, and for isotope tracing of anthropogenic Hg emissions.

Metal release into the environment from anthropogenic activities may endanger ecosystems and human health. However, identifying and quantifying anthropogenic metal bioaccumulation in organisms remain a challenging task. In this work, we assess Cu isotopes in Pacific oysters (C. gigas) as a new tool for monitoring anthropogenic Cu bioaccumulation into marine environments. Arcachon Bay was taken as a natural laboratory due to its increasing contamination by Cu, and its relevance as a prominent shellfish production area. Here, we transplanted 18-month old oysters reared in an oceanic neighbor area into two Arcachon Bay mariculture sites under different exposure levels to continental Cu inputs. At the end of their 12-month long transplantation period, the oysters’ Cu body burdens had increased, and was shifted toward more positive δ⁶⁵Cu values. The gradient of Cu isotope compositions observed for oysters sampling stations was consistent with relative geographic distance and exposure intensities to unknown continental Cu sources. A binary isotope mixing model based on experimental data allowed to estimate the Cu continental fraction bioaccumulated in the transplanted oysters. The positive δ⁶⁵Cu values and high bioaccumulated levels of Cu in transplanted oysters support that continental emissions are dominantly anthropogenic. However, identifying specific pollutant coastal source remained unelucidated mostly due to their broader and overlapping isotope signatures and potential post-depositional Cu isotope fractionation processes. Further investigations on isotope fractionation of Cu-based compounds in an aqueous medium may improve Cu source discrimination. Thus, using Cu as an example, this work combines for the first time a well-known caged bivalve approach with metal stable isotope techniques for monitoring and quantifying the bioaccumulation of anthropogenic metal into marine environments. Also, it states the main challenges to pinpoint specific coastal anthropogenic sources utilizing this approach and provides the perspectives for further studies to overcome them.

Compound-specific stable isotope analysis of micropollutants has become an established method for the qualitative and quantitative assessment of biodegradation in the field. However, many of environmental factors may have an influence on the observed isotope fractionation. Herein, we investigate the impact of substrate concentration on the observed enrichment factor derived from Rayleigh plot of batch laboratory experiments conducted to measure the atrazine carbon isotope fractionation of Rhizobium sp. CX-Z subjected to the different initial concentration level of atrazine. The Rayleigh plot (changes in bulk concentration vs. isotopic composition) derived from batch experiments shown divergence from the linear relation towards the end of degradation, confirming bioavailability of atrazine changed along with the decay of substrate concentration, consequently, influenced the isotope fractionation and lowered the observed enrichment factor. When microbial degradation is coupled to a mass transfer step limiting the bioavailability of substrate, the observed enrichment factor displays a dependence on initial atrazine concentration. Observed enrichment factors (ε) (absolute value) derived from the low concentration (i.e. 9.5 μM) are below 3.5‰ to the value of −5.4‰ determined at high bioavailability (membrane-free cells). The observed enrichment factor depended significantly on the atrazine concentration, indicating the concentration level and the bioavailability of a substrate in realistic environments should be considered during the assessment of microbial degradation or in situ bioremediation based on compound-specific stable isotope analysis (CSIA) method.

Microbial degradation is an important pathway for the attenuation of polybrominated diphenyl ethers (PBDEs) in natural soils. In this study, the compound-specific stable isotope analysis (CSIA) was applied to characterize microbial degradation of BDE-153, one of the prevailing and toxic PBDE congeners, in natural wetland soils. During the 45-day incubation, the residual percentages of BDE-153 decreased to 67.9% and 73.6% in non-sterilized soils spiked with 1.0 and 5.0 μg/g, respectively, which were both much lower than those in sterilized soils (96.0% and 97.2%). This result indicated that microbial degradation could accelerate BDE-153 elimination in wetland soils. Meanwhile, the significant carbon isotope fractionation was observed in non-sterilized soils, with δ¹³C of BDE-153 shifting from −29.4‰ to −26.7‰ for 1.0 μg/g and to −27.2‰ for 5.0 μg/g, respectively, whilst not in sterilized soils. This phenomenon indicated microbial degradation could induce stable carbon isotope fractionation of BDE-153. The carbon isotope enrichment factor (εc) for BDE-153 microbial degradation was first determined as −7.58‰, which could be used to assess the microbial degradation and bioavailability of BDE-153 in wetland soils. Based on δ¹³C and εc, the new methods were developed to dynamically and quantitatively estimate degradation degree and bioavailability of BDE-153 during degradation process, respectively, which could exclude interference of physical processes. This work revealed that CSIA was a promising method to investigate in situ microbial degradation of PBDEs in field studies.

Cd in soils might be taken up by plants, enter the food chain and endanger human health. This study investigates the isotopic fractionation of major processes during the Cd transfer from soils to cereal grains. Thereto, soil, soil solution, wheat and barley plants (roots, straw and grains) were sampled in the field at three study sites during two vegetation periods. Cd concentrations and δ¹¹⁴/¹¹⁰Cd values were determined in all samples. The composition of the soil solution was analyzed and the speciation of the dissolved Cd was modelled. Isotopic fractionation between soils and soil solutions (Δ¹¹⁴/¹¹⁰Cd₂₀₋₅₀cₘ₋ₛₒᵢₗ ₛₒₗᵤₜᵢₒₙ = −0.61 to −0.68‰) was nearly constant among the three soils. Cd isotope compositions in plants were heavier than in soils (Δ¹¹⁴/¹¹⁰Cd₀₋₂₀cₘ₋ₚₗₐₙₜₛ = −0.55 to −0.31‰) but lighter than in soil solutions (Δ¹¹⁴/¹¹⁰Cdₛₒᵢₗ ₛₒₗᵤₜᵢₒₙ₋ₚₗₐₙₜₛ = 0.06–0.36‰) and these differences correlated with Cd plant-uptake rates. In a conceptual model, desorption from soil, soil solution speciation, adsorption on root surfaces, diffusion, and plant uptake were identified as the responsible processes for the Cd isotope fractionation between soil, soil solution and plants whereas the first two processes dominated over the last three processes. Within plants, compartments with lower Cd concentrations were enriched in light isotopes which might be a consequence of Cd retention mechanisms, following a Rayleigh fractionation, in which barley cultivars were more efficient than wheat cultivars.

Excess ammonia (NH₃) emissions and deposition can have negative effects on air quality and terrestrial ecosystems. Identifying NH₃ sources is a critical step for effectively reducing NH₃ emissions, which are generally unregulated around the world. Stable nitrogen isotopes (δ¹⁵N) of ammonium (NH₄⁺) in precipitation have been directly used to partition NH₃ sources. However, nitrogen isotope fractionation during atmospheric processes from NH₃ sources to sinks has been previously overlooked. Here we measured δ¹⁵NNH₄⁺ in precipitation on a daily basis at a rural forested site in Northeast China over three years to examine its seasonal pattern and attempt to constrain the NH₃ sources. We found that the NH₄⁺ concentrations in precipitation ranged from 5 to 1265 μM, and NH₄⁺ accounted for 65% of the inorganic nitrogen deposition (20.0 kg N ha⁻¹ yr⁻¹) over the study period. The δ¹⁵N values of NH₄⁺ fluctuated from −24.6 to +16.2‰ (average −6.5‰) and showed a repeatable seasonal pattern with higher values in summer (average −2.3‰) than in winter (average −16.4‰), which could not be explained by only the seasonal changes in the NH₃ sources. Our results suggest that in addition to the NH₃ sources, isotope equilibrium fractionation contributed to the seasonal pattern of δ¹⁵NNH₄⁺ in precipitation, and thus, nitrogen isotope fractionation should be considered when partitioning NH₃ sources based on δ¹⁵NNH₄⁺ in precipitation.

Microbial degradation of phenol and cresols can occur under oxic and anoxic conditions by different degradation pathways. One recent technique to take insight into reaction mechanisms is compound-specific isotope analysis (CSIA). While enzymes and reaction mechanisms of several degradation pathways have been characterized in (bio)chemical studies, associated isotope fractionation patterns have been rarely reported, possibly due to constraints in current analytical methods. In this study, carbon enrichment factors and apparent kinetic isotope effects (AKIEc) of the initial steps of different aerobic and anaerobic phenol and cresols degradation pathways were analyzed by isotope ratio mass spectrometry connected with liquid chromatography (LC-IRMS). Significant isotope fractionation was detected for aerobic ring hydroxylation, anoxic side chain hydroxylation, and anoxic fumarate addition, while anoxic carboxylation reactions produced small and inconsistent fractionation. The results suggest that several microbial degradation pathways of phenol and cresols are detectable in the environment by CSIA.

The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. To demonstrate specific features of the modeling approach, we simulated the degradation of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model accurately reproduces the multi-element isotope data observed in previous experimental studies. Furthermore, it precisely captures the dual element isotope trends characteristic of different reaction pathways as well as their range of variation consistent with observed bulk isotope fractionation. It was also possible to directly validate the model capability to predict the evolution of position-specific isotope ratios with available experimental data. Therefore, the approach is useful both for a mechanism-based evaluation of experimental results and as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available.