Exploring trends of C and N isotope fractionation to trace transformation reactions of diclofenac in natural and engineered systems
Although diclofenac ranks among the most frequently detected pharmaceuticals in the urban water cycle, its environmental transformation reactions remain imperfectly understood. Biodegradation-induced changes in 15N/14N ratios (εN = −7.1‰ ± 0.4‰) have indicated that compound-specific isotope analysis (CSIA) may detect diclofenac degradation. This singular observation warrants exploration for further transformation reactions. The present study surveys carbon and nitrogen isotope fractionation in other environmental and engineered transformation reactions of diclofenac. While carbon isotope fractionation was generally small, observed nitrogen isotope fractionation in degradation by MnO2 (εN = −7.3‰ ± 0.3‰), photolysis (εN = +1.9‰ ± 0.1‰), and ozonation (εN = +1.5‰ ± 0.2‰) revealed distinct trends for different oxidative transformation reactions. The small, secondary isotope effect associated with ozonation suggests an attack of O3 in a molecular position distant from the N atom. Model reactants for outer-sphere single electron transfer generated large inverse nitrogen isotope fractionation (εN = +5.7‰ ± 0.3‰), ruling out this mechanism for biodegradation and transformation by MnO2. In a river model, isotope fractionation-derived degradation estimates agreed well with concentration mass balances, providing a proof-of-principle validation for assessing micropollutant degradation in river sediment. Our study highlights the prospect of combining CSIA with transformation product analysis for a better assessment of transformation reactions within the environmental life of diclofenac.
The sources of atmospheric black carbon at a European gateway to the ArcticDownload
Black carbon (BC) aerosols from incomplete combustion of biomass and fossil fuel contribute to Arctic climate warming. Models—seeking to advise mitigation policy—are challenged in reproducing observations of seasonally varying BC concentrations in the Arctic air. Here we compare year-round observations of BC and its d13C/D14C-diagnosed sources in Arctic Scandinavia, with tailored simulations from an atmospheric transport model. The model predictions for this European gateway to the Arctic are greatly improved when the emission inventory of anthropogenic sources is amended by satellite-derived estimates of BC emis- sions from fires. Both BC concentrations (R2=0.89, P<0.05) and source contributions (R2=0.77, P<0.05) are accurately mimicked and linked to predominantly European emis- sions. This improved model skill allows for more accurate assessment of sources and effects of BC in the Arctic, and a more credible scientific underpinning of policy efforts aimed at efficiently reducing BC emissions reaching the European Arctic.
Cocaine and cannabinoids in the atmosphere of Northern Europe cities, comparison with Southern Europe and wastewater analysis
This study reports the first investigation of atmospheric illicit drug concentrations in Northern Europe usingmeasurements
of cocaine and cannabinoids in Amsterdam, London and Stockholm. Further, these measurements
were compared to those made in Rome to explore the geographical and inter-city variability. Co-located measurements
of atmospheric particulate mass and PAHs were used to help describe and interpret the illicit drug
measurements with respect to atmospheric dispersion. Cocaine concentrations ranged from 0.03 to 0.14 ng/m3
in Amsterdam, from 0.02 to 0.33 ng/m3 in London and were below quantification limit (3 pg/m3) in Stockholm.
Cannabinol was the only cannabinoidmolecule detected in the three cities. During this campaign, London reported
the highest concentrations of cocaine and meaningful differences were detected between the urban background
and city centre London sites. Mean cocaine concentrations measured in Amsterdam during March
2011 were also compared with those measured simultaneously in eight Italian cities. The cocaine concentration
inAmsterdamwas comparable to that measured at an urban background inMilan and at a densely populated site
in Florence. Although correlating atmospheric concentrations directlywith drug prevalence is not possible using
current data, links between concentrations of cocaine and estimates of abuse prevalence assessed by the more
routinely usedwastewater analysiswere also examined. A statistically significant correlationwas found between
the two sets of data (R2=0.66; p=0.00131). Results confirmed that meteorology, population rate and habits of
consumption influence the atmospheric concentrations of drugs. If these confounding factors were better controlled
for, the techniques described here could became an easy and cost effective tool to index the impact of cocaine
abuse in the area; especially where local hot spots need to be identified.
Fate of terrigenous organic matter across the Laptev Sea from the mouth of the Lena River to the deep sea of the Arctic interior
Ongoing global warming in high latitudes may cause an increasing supply of permafrost-derived organic carbon through both river discharge and coastal erosion to the Arctic shelves. Mobilized permafrost carbon can be either buried in sediments, transported to the deep sea or degraded to CO2 and outgassed, potentially constituting a positive feedback to climate change. This study aims to assess the fate of terrigenous organic carbon (TerrOC) in the Arctic marine environment by exploring how it changes in concentration, composition and degradation status across the wide Laptev Sea shelf. We analyzed a suite of terrestrial biomarkers as well as source-diagnostic bulk carbon isotopes (δ13C, Δ14C) in surface sediments from a Laptev Sea transect spanning more than 800 km from the Lena River mouth (< 10 m water depth) across the shelf to the slope and rise (2000–3000 m water depth). These data provide a broad view on different TerrOC pools and their behavior during cross-shelf transport. The concentrations of lignin phenols, cutin acids and high-molecular-weight (HMW) wax lipids (tracers of vascular plants) decrease by 89–99 % along the transect. Molecular-based degradation proxies for TerrOC (e.g., the carbon preference index of HMW lipids, the HMW acids ∕ alkanes ratio and the acid ∕ aldehyde ratio of lignin phenols) display a trend to more degraded TerrOC with increasing distance from the coast. We infer that the degree of degradation of permafrost-derived TerrOC is a function of the time spent under oxic conditions during protracted cross-shelf transport. Future work should therefore seek to constrain cross-shelf transport times in order to compute a TerrOC degradation rate and thereby help to quantify potential carbon–climate feedbacks.
Suspect screening of OH-PAHs and non-target screening of other organic compounds in wood smoke particles using HR-Orbitrap-MS
Wood combustion has been shown to contribute significantly to emissions of polycyclic aromatic hydrocarbons and hydroxylated polycyclic aromatic hydrocarbons, compounds with toxic and carcinogenic properties. However, only a small number of hydroxylated polycyclic aromatic hydrocarbons have been determined in particles from wood combustion, usually compounds with available reference standards. In this present study, suspect and non-target screening strategies were applied to characterize the wood smoke particles from four different wood types and two combustion conditions with respect to hydroxylated polycyclic aromatic hydrocarbons and other organic compounds. In the suspect screening, 32 peaks corresponding to 12 monohydroxylated masses were tentatively identified by elemental composition assignments and matching of isotopic pattern and fragments. More than one structure was suggested for most of the measured masses. Statistical analysis was performed on the non-target screening data in order to single out significant peaks having intensities that depend on the wood type and/or combustion condition. Significant peaks were found in both negative and positive ionization modes, with unique peaks for each wood type and combustion condition, as well as a combination of both factors. Furthermore, structural elucidation of some peaks was done by comparing the spectra in the samples with spectra found in the spectral databases. Six compounds were tentatively identified in positive ionization mode, and 19 in negative ionization mode. The results in this present study demonstrate that there are significant overall differences in the chemistry of wood smoke particles that depends on both the wood type and the combustion condition used.
Implementing systematic review techniques in chemical risk assessment: Challenges, opportunities and recommendations
Systematic review (SR) is a rigorous, protocol-driven approach designed to minimise error and bias when summarising the body of research evidence relevant to a specific scientific question. Taking as a comparator the use of SR in synthesising research in healthcare, we argue that SR methods could also pave the way for a “step change” in the transparency, objectivity and communication of chemical risk assessments (CRA) in Europe and elsewhere. We suggest that current controversies around the safety of certain chemicals are partly due to limitations in current CRA procedures which have contributed to ambiguity about the health risks posed by these substances. We present an overview of how SR methods can be applied to the assessment of risks from chemicals, and indicate how challenges in adapting SR methods from healthcare research to the CRA context might be overcome. Regarding the latter, we report the outcomes from a workshop exploring how to increase uptake of SR methods, attended by experts representing a wide range of fields related to chemical toxicology, risk analysis and SR. Priorities which were identified include: the conduct of CRA-focused prototype SRs; the development of a recognised standard of reporting and conduct for SRs in toxicology and CRA; and establishing a network to facilitate research, communication and training in SR methods. We see this paper as a milestone in the creation of a research climate that fosters communication between experts in CRA and SR and facilitates wider uptake of SR methods into CRA.
Weight of Evidence evaluation and Systematic Review in EU chemical risk assessment: Foundation is laid but guidance is needed
The aim of this review was to investigate if and how the application of weight of evidence (WoE) evaluation or systematic review (SR) in chemical risk assessment is promoted within different regulatory frameworks in the European Union. Legislative and relevant guidance documents within nine regulatory frameworks were scrutinized and compared. WoE evaluation or SR is promoted in seven of the investigated frameworks but sufficient guidance for how to perform these processes is generally lacking. None of the investigated frameworks give enough guidance for generating robust and reproducible WoE evaluations or SRs. In conclusion, the foundation for use of WoE evaluation and SR is laid in the majority of the investigated frameworks, but there is a need to provide more structured and detailed guidance. In order to make the process of developing guidance as efficient as possible, and to ensure smooth transfer of risk assessment's between frameworks if a chemical is risk assessed both as, for example, a biocide and an industrial chemical, it is recommended that guidance is developed jointly by the European regulatory agencies.
Study sensitivity: Evaluating the ability to detect effects in systematic reviews of chemical exposures
A critical step in systematic reviews of potential health hazards is the structured evaluation of the strengths and weaknesses of the included studies; risk of bias is a term often used to represent this process, specifically with respect to the evaluation of systematic errors that can lead to inaccurate (biased) results (i.e. focusing on internal validity). Systematic review methods developed in the clinical medicine arena have been adapted for use in evaluating environmental health hazards; this expansion raises questions about the scope of risk of bias tools and the extent to which they capture the elements that can affect the interpretation of results from environmental and occupational epidemiology studies and in vivo animal toxicology studies, (the studies typically available for assessment of risk of chemicals). One such element, described here as “sensitivity”, is a measure of the ability of a study to detect a true effect or hazard. This concept is similar to the concept of the sensitivity of an assay; an insensitive study may fail to show a difference that truly exists, leading to a false conclusion of no effect. Factors relating to study sensitivity should be evaluated in a systematic manner with the same rigor as the evaluation of other elements within a risk of bias framework. We discuss the importance of this component for the interpretation of individual studies, examine approaches proposed or in use to address it, and describe how it relates to other evaluation components. The evaluation domains contained within a risk of bias tool can include, or can be modified to include, some features relating to study sensitivity; the explicit inclusion of these sensitivity criteria with the same rigor and at the same stage of study evaluation as other bias-related criteria can improve the evaluation process. In some cases, these and other features may be better addressed through a separate sensitivity domain. The combined evaluation of risk of bias and sensitivity can be used to identify the most informative studies, to evaluate the confidence of the findings from individual studies and to identify those study elements that may help to explain heterogeneity across the body of literature.
Permafrost Sub-grid Heterogeneity of Soil Properties Key for 3-D Soil Processes and Future Climate Projections
There are massive carbon stocks stored in permafrost-affected soils due to the 3-D soil movement process called cryoturbation. For a reliable projection of the past, recent and future Arctic carbon balance, and hence climate, a reliable concept for representing cryoturbation in a land surface model (LSM) is required. The basis of the underlying transport processes is pedon-scale heterogeneity of soil hydrological and thermal properties as well as insulating layers, such as snow and vegetation. Today we still lack a concept of how to reliably represent pedon-scale properties and processes in a LSM. One possibility could be a statistical approach. This perspective paper demonstrates the importance of sub-grid heterogeneity in permafrost soils as a pre-requisite to implement any lateral transport parametrization. Representing such heterogeneity at the sub-pixel size of a LSM is the next logical step of model advancements. As a result of a theoretical experiment, heterogeneity of thermal and hydrological soil properties alone lead to a remarkable initial sub-grid range of subsoil temperature of 2°C, and active-layer thickness of 150 cm in East Siberia. These results show the way forward in representing combined lateral and vertical transport of water and soil in LSMs.
Ubiquity and impact of thin mid-level clouds in the tropics
Clouds are crucial for Earth’s climate and radiation budget. Great attention has been paid to low, high and vertically thick tropospheric clouds such as stratus, cirrus and deep convective clouds. However, much less is known about tropospheric mid-level clouds as these clouds are challenging to observe in situ and difficult to detect by remote sensing techniques. Here we use Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) satellite observations to show that thin mid-level clouds (TMLCs) are ubiquitous in the tropics. Supported by high-resolution regional model simulations, we find that TMLCs are formed by detrainment from convective clouds near the zero-degree isotherm. Calculations using a radiative transfer model indicate that tropical TMLCs have a cooling effect on climate that could be as large in magnitude as the warming effect of cirrus. We conclude that more effort has to be made to understand TMLCs, as their influence on cloud feedbacks, heat and moisture transport, and climate sensitivity could be substantial.