Resistance as a factor in environmental exposure of anticoagulant rodenticides: a modelling approach

Anticoagulant rodenticide (AR) resistance in Norway rat populations has been a problem for fifty years, however its impact on non-target species, particularly predatory and scavenging animals has received little attention. Field trials were conducted on farms in Germany and England where resistance to anticoagulant rodenticides had been confirmed. Resistance is conferred by different mutations of the VKORC1 gene in each of these regions: tyrosine139cysteine in Germany and leucine120glutamine in England. A modelling approach was used to study the transference of the anticoagulants into the environment during treatments for Norway rat control. Baiting with brodifacoum resulted in lower levels of AR entering the food chain via the rats and lower numbers of live rats carrying residues during and after the trials due to its lower application rate and efficacy against resistant rats. Bromadiolone and difenacoum resulted in markedly higher levels of AR uptake into the rat population and larger numbers of live rats carrying residues during the trials and for long periods after the baiting period. Neither bromadiolone nor difenacoum provided full control on any of the treated farms. In resistant areas where ineffective compounds are used there is the potential for higher levels of AR exposure to non-target animals, particularly predators of rats and scavengers of rat carcasses. Thus, resistance influences the total amount of AR available to non-targets and should be considered when dealing with rat infestations, as resistance-breakers may present a lower risk to wildlife.

Human red blood cells at work: identification and visualization of erythrocytic eNOS activity in health and disease

A nitric oxide synthase (NOS)-like activity has been demonstrated in human red blood cells (RBCs), but doubts about its functional significance, isoform identity and disease relevance remain. Using flow cytometry in combination with the NO-imaging probe DAF-FM we find that all blood cells form NO intracellularly, with a rank order of monocytes > neutrophils > lymphocytes > RBCs > platelets. The observation of a NO-related fluorescence within RBCs was unexpected given the abundance of the NO-scavenger oxyhemoglobin. Constitutive normoxic NO formation was abolished by NOS inhibition and intracellular NO scavenging, confirmed by laser-scanning microscopy and unequivocally validated by detection of the DAF-FM reaction product with NO using HPLC and LC-MS/MS. Employing immunoprecipitation, ESI-MS/MS-based peptide sequencing and enzymatic assay we further demonstrate that human RBCs contain an endothelial NOS (eNOS) that converts L-3H-Arginine to L-3H-Citrulline in a Ca2+/Calmodulin-dependent fashion. Moreover, in patients with coronary artery disease, red cell eNOS expression and activity are both lower than in age-matched healthy individuals and correlate with the degree of endothelial dysfunction. Thus, human RBCs constitutively produce NO under normoxic conditions via an active eNOS isoform the activity of which is compromised in patients with coronary artery disease.

Triboelectric charging of volcanic ash from the 2011 Grímsvötn eruption

The plume from the 2011 eruption of Grímsvötn was highly electrically charged, as shown by the considerable lightning activity measured by the United Kingdom Met Office’s low-frequency lightning detection network. Previous measurements of volcanic plumes have shown that ash particles are electrically charged up to hundreds of kilometers away from the vent, which indicates that the ash continues to charge in the plume [R. G. Harrison, K. A. Nicoll, Z. Ulanowski, and T. A. Mather, Environ. Res. Lett. 5 024004 (2010); H. Hatakeyama J. Meteorol. Soc. Jpn. 27 372 (1949)]. In this Letter, we study triboelectric charging of different size fractions of a sample of volcanic ash experimentally. Consistently with previous work, we find that the particle size distribution is a determining factor in the charging. Specifically, our laboratory experiments demonstrate that the normalized span of the particle size distribution plays an important role in the magnitude of charging generated. The influence of the normalized span on plume charging suggests that all ash plumes are likely to be charged, with implications for remote sensing and plume lifetime through scavenging effects.

Modelling the effects of gravity waves on stratocumulus clouds observed during VOCALS-UK

During the VOCALS campaign spaceborne satellite observations showed that travelling gravity wave packets, generated by geostrophic adjustment, resulted in perturbations to marine boundary layer (MBL) clouds over the south-east Pacific Ocean (SEP). Often, these perturbations were reversible in that passage of the wave resulted in the clouds becoming brighter (in the wave crest), then darker (in the wave trough) and subsequently recovering their properties after the passage of the wave. However, occasionally the wave packets triggered irreversible changes to the clouds, which transformed from closed mesoscale cellular convection to open form. In this paper we use large eddy simulation (LES) to examine the physical mechanisms that cause this transition. Specifically, we examine whether the clearing of the cloud is due to (i) the wave causing additional cloud-top entrainment of warm, dry air or (ii) whether the additional condensation of liquid water onto the existing drops and the subsequent formation of drizzle are the important mechanisms. We find that, although the wave does cause additional drizzle formation, this is not the reason for the persistent clearing of the cloud; rather it is the additional entrainment of warm, dry air into the cloud followed by a reduction in longwave cooling, although this only has a significant effect when the cloud is starting to decouple from the boundary layer. The result in this case is a change from a stratocumulus to a more patchy cloud regime. For the simulations presented here, cloud condensation nuclei (CCN) scavenging did not play an important role in the clearing of the cloud. The results have implications for understanding transitions between the different cellular regimes in marine boundary layer (MBL) clouds.

Quantifying the importance of galactic cosmic rays in cloud microphysical processes

Galactic Cosmic Rays are one of the major sources of ion production in the troposphere and stratosphere. Recent studies have shown that ions form electrically charged clusters which may grow to become cloud droplets. Aerosol particles charge by the attachment of ions and electrons. The collision efficiency between a particle and a water droplet increases, if the particle is electrically charged, and thus aerosol-cloud interactions can be enhanced. Because these microphysical processes may change radiative properties of cloud and impact Earth's climate it is important to evaluate these processes' quantitative effects. Five different models developed independently have been coupled to investigate this. The first model estimates cloud height from dew point temperature and the temperature profile. The second model simulates the cloud droplet growth from aerosol particles using the cloud parcel concept. In the third model, the scavenging rate of the aerosol particles is calculated using the collision efficiency between charged particles and droplets. The fourth model calculates electric field and charge distribution on water droplets and aerosols within cloud. The fifth model simulates the global electric circuit (GEC), which computes the conductivity and ionic concentration in the atmosphere in altitude range 0–45 km. The first four models are initially coupled to calculate the height of cloud, boundary condition of cloud, followed by growth of droplets, charge distribution calculation on aerosols and cloud droplets and finally scavenging. These models are incorporated with the GEC model. The simulations are verified with experimental data of charged aerosol for various altitudes. Our calculations showed an effect of aerosol charging on the CCN concentration within the cloud, due to charging of aerosols increase the scavenging of particles in the size range 0.1 µm to 1 µm.

Impact of vegetation and preferential source areas on global dust aerosol: results from a model study

[1] We present a model of the dust cycle that successfully predicts dust emissions as determined by land surface properties, monthly vegetation and snow cover, and 6-hourly surface wind speeds for the years 1982–1993. The model takes account of the role of dry lake beds as preferential source areas for dust emission. The occurrence of these preferential sources is determined by a water routing and storage model. The dust source scheme also explicitly takes into account the role of vegetation type as well as monthly vegetation cover. Dust transport is computed using assimilated winds for the years 1987–1990. Deposition of dust occurs through dry and wet deposition, where subcloud scavenging is calculated using assimilated precipitation fields. Comparison of simulated patterns of atmospheric dust loading with the Total Ozone Mapping Spectrometer satellite absorbing aerosol index shows that the model produces realistic results from daily to interannual timescales. The magnitude of dust deposition agrees well with sediment flux data from marine sites. Emission of submicron dust from preferential source areas are required for the computation of a realistic dust optical thickness. Sensitivity studies show that Asian dust source strengths are particularly sensitive to the seasonality of vegetation cover.

The role of dust in climate changes today, at the last glacial maximum and in the future.

Natural mineral aerosol (dust) is an active component of the climate system and plays multiple roles in mediating physical and biogeochemical exchanges between the atmosphere, land surface and ocean. Changes in the amount of dust in the atmosphere are caused both by changes in climate (precipitation, wind strength, regional moisture balance) and changes in the extent of dust sources caused by either anthropogenic or climatically induced changes in vegetation cover. Models of the global dust cycle take into account the physical controls on dust deflation from prescribed source areas (based largely on soil wetness and vegetation cover thresholds), dust transport within the atmospheric column, and dust deposition through sedimentation and scavenging by precipitation. These models successfully reproduce the first-order spatial and temporal patterns in atmospheric dust loading under modern conditions. Atmospheric dust loading was as much as an order-of-magnitude larger than today during the last glacial maximum (LGM). While the observed increase in emissions from northern Africa can be explained solely in terms of climate changes (colder, drier and windier glacial climates), increased emissions from other regions appear to have been largely a response to climatically induced changes in vegetation cover and hence in the extent of dust source areas. Model experiments suggest that the increased dust loading in tropical regions had an effect on radiative forcing comparable to that of low glacial CO2 levels. Changes in land-use are already increasing the dust loading of the atmosphere. However, simulations show that anthropogenically forced climate changes substantially reduce the extent and productivity of natural dust sources. Positive feedbacks initiated by a reduction of dust emissions from natural source areas on both radiative forcing and atmospheric CO2 could substantially mitigate the impacts of land-use changes, and need to be considered in climate change assessments.

An AeroCom assessment of black carbon in Arctic snow and sea ice

Though many global aerosols models prognose surface deposition, only a few models have been used to directly simulate the radiative effect from black carbon (BC) deposition to snow and sea ice. Here, we apply aerosol deposition fields from 25 models contributing to two phases of the Aerosol Comparisons between Observations and Models (AeroCom) project to simulate and evaluate within-snow BC concentrations and radiative effect in the Arctic. We accomplish this by driving the offline land and sea ice components of the Community Earth System Model with different deposition fields and meteorological conditions from 2004 to 2009, during which an extensive field campaign of BC measurements in Arctic snow occurred. We find that models generally underestimate BC concentrations in snow in northern Russia and Norway, while overestimating BC amounts elsewhere in the Arctic. Although simulated BC distributions in snow are poorly correlated with measurements, mean values are reasonable. The multi-model mean (range) bias in BC concentrations, sampled over the same grid cells, snow depths, and months of measurements, are −4.4 (−13.2 to +10.7) ng g−1 for an earlier phase of AeroCom models (phase I), and +4.1 (−13.0 to +21.4) ng g−1 for a more recent phase of AeroCom models (phase II), compared to the observational mean of 19.2 ng g−1. Factors determining model BC concentrations in Arctic snow include Arctic BC emissions, transport of extra-Arctic aerosols, precipitation, deposition efficiency of aerosols within the Arctic, and meltwater removal of particles in snow. Sensitivity studies show that the model–measurement evaluation is only weakly affected by meltwater scavenging efficiency because most measurements were conducted in non-melting snow. The Arctic (60–90° N) atmospheric residence time for BC in phase II models ranges from 3.7 to 23.2 days, implying large inter-model variation in local BC deposition efficiency. Combined with the fact that most Arctic BC deposition originates from extra-Arctic emissions, these results suggest that aerosol removal processes are a leading source of variation in model performance. The multi-model mean (full range) of Arctic radiative effect from BC in snow is 0.15 (0.07–0.25) W m−2 and 0.18 (0.06–0.28) W m−2 in phase I and phase II models, respectively. After correcting for model biases relative to observed BC concentrations in different regions of the Arctic, we obtain a multi-model mean Arctic radiative effect of 0.17 W m−2 for the combined AeroCom ensembles. Finally, there is a high correlation between modeled BC concentrations sampled over the observational sites and the Arctic as a whole, indicating that the field campaign provided a reasonable sample of the Arctic.

Widespread supplementary feeding in domestic gardens explains the return of reintroduced Red Kites Milvus milvus to an urban area

Reintroductions are used worldwide to mitigate biodiversity loss. One prominent case is a charismatic raptor of conservation concern, the Red Kite Milvus milvus. This species has been reintroduced across the UK over the last 25 years following its near extinction after centuries of persecution. The species was not expected to recolonize urban areas; its historical association with human settlements is attributed to scavenging on human waste and refuse, a resource now greatly reduced on the streets of modern Western cities. However, the species has become a common day-time visitor to a large conurbation centred on the town of Reading, southern England, approximately 20 km from the first English reintroduction site. Given a near-absence of breeding and roost sites, we investigated foraging opportunities and habitat associations that might explain use by Red Kites of this urban area. Surveys of discarded human foods and road-kill suggested that these could support at most 13−29 kites/day. Face-to-face surveys of a cross-section of residents revealed that 4.5% (equivalent to 4349 households) provided supplementary food for kites. Using estimates of per-household resource provision from another study, we calculated that this level is potentially sufficient to provision 142−320 kites, a substantial proportion of the total estimated to visit the conurbation each day (between 140 and 440). Road transects found positive associations between Red Kites and residential areas. We therefore suggest that the decision made by thousands of individuals to provide supplementary food for Red Kites is the primary factor explaining their day-time abundance in this urban area.

Clouds, aerosols, and precipitation in the marine boundary layer: an ARM Mobile Facility Deployment

The Clouds, Aerosol, and Precipitation in the Marine Boundary Layer (CAP-MBL) deployment at Graciosa Island in the Azores generated a 21-month (April 2009–December 2010) comprehensive dataset documenting clouds, aerosols, and precipitation using the Atmospheric Radiation Measurement Program (ARM) Mobile Facility (AMF). The scientific aim of the deployment is to gain improved understanding of the interactions of clouds, aerosols, and precipitation in the marine boundary layer. Graciosa Island straddles the boundary between the subtropics and midlatitudes in the northeast Atlantic Ocean and consequently experiences a great diversity of meteorological and cloudiness conditions. Low clouds are the dominant cloud type, with stratocumulus and cumulus occurring regularly. Approximately half of all clouds contained precipitation detectable as radar echoes below the cloud base. Radar and satellite observations show that clouds with tops from 1 to 11 km contribute more or less equally to surface-measured precipitation at Graciosa. A wide range of aerosol conditions was sampled during the deployment consistent with the diversity of sources as indicated by back-trajectory analysis. Preliminary findings suggest important two-way interactions between aerosols and clouds at Graciosa, with aerosols affecting light precipitation and cloud radiative properties while being controlled in part by precipitation scavenging. The data from Graciosa are being compared with short-range forecasts made with a variety of models. A pilot analysis with two climate and two weather forecast models shows that they reproduce the observed time-varying vertical structure of lower-tropospheric cloud fairly well but the cloud-nucleating aerosol concentrations less well. The Graciosa site has been chosen to be a permanent fixed ARM site that became operational in October 2013.

Key bioactive reaction products of the NO/H2S interaction are S/N-hybrid species, polysulfides, and nitroxyl

Experimental evidence suggests that nitric oxide (NO) and hydrogen sulfide (H2S) signaling pathways are intimately intertwined, with mutual attenuation or potentiation of biological responses in the cardiovascular system and elsewhere. The chemical basis of this interaction is elusive. Moreover, polysulfides recently emerged as potential mediators of H2S/sulfide signaling, but their biosynthesis and relationship to NO remain enigmatic. We sought to characterize the nature, chemical biology, and bioactivity of key reaction products formed in the NO/sulfide system. At physiological pH, we find that NO and sulfide form a network of cascading chemical reactions that generate radical intermediates as well as anionic and uncharged solutes, with accumulation of three major products: nitrosopersulfide (SSNO−), polysulfides, and dinitrososulfite N-nitrosohydroxylamine-N-sulfonate (SULFI/NO), each with a distinct chemical biology and in vitro and in vivo bioactivity. SSNO− is resistant to thiols and cyanolysis, efficiently donates both sulfane sulfur and NO, and potently lowers blood pressure. Polysulfides are both intermediates and products of SSNO− synthesis/decomposition, and they also decrease blood pressure and enhance arterial compliance. SULFI/NO is a weak combined NO/nitroxyl donor that releases mainly N2O on decomposition; although it affects blood pressure only mildly, it markedly increases cardiac contractility, and formation of its precursor sulfite likely contributes to NO scavenging. Our results unveil an unexpectedly rich network of coupled chemical reactions between NO and H2S/sulfide, suggesting that the bioactivity of either transmitter is governed by concomitant formation of polysulfides and anionic S/N-hybrid species. This conceptual framework would seem to offer ample opportunities for the modulation of fundamental biological processes governed by redox switching and sulfur trafficking.

Interaction of plant growth regulators and reactive oxygen species to regulate petal senescence in wallflowers (Erysimum linifolium)

Background In many species floral senescence is coordinated by ethylene. Endogenous levels rise, and exogenous application accelerates senescence. Furthermore, floral senescence is often associated with increased reactive oxygen species, and is delayed by exogenously applied cytokinin. However, how these processes are linked remains largely unresolved. Erysimum linifolium (wallflower) provides an excellent model for understanding these interactions due to its easily staged flowers and close taxonomic relationship to Arabidopsis. This has facilitated microarray analysis of gene expression during petal senescence and provided gene markers for following the effects of treatments on different regulatory pathways. Results In detached Erysimum linifolium (wallflower) flowers ethylene production peaks in open flowers. Furthermore senescence is delayed by treatments with the ethylene signalling inhibitor silver thiosulphate, and accelerated with ethylene released by 2-chloroethylphosphonic acid. Both treatments with exogenous cytokinin, or 6-methyl purine (which is an inhibitor of cytokinin oxidase), delay petal senescence. However, treatment with cytokinin also increases ethylene biosynthesis. Despite the similar effects on senescence, transcript abundance of gene markers is affected differentially by the treatments. A significant rise in transcript abundance of WLS73 (a putative aminocyclopropanecarboxylate oxidase) was abolished by cytokinin or 6-methyl purine treatments. In contrast, WFSAG12 transcript (a senescence marker) continued to accumulate significantly, albeit at a reduced rate. Silver thiosulphate suppressed the increase in transcript abundance both of WFSAG12 and WLS73. Activity of reactive oxygen species scavenging enzymes changed during senescence. Treatments that increased cytokinin levels, or inhibited ethylene action, reduced accumulation of hydrogen peroxide. Furthermore, although auxin levels rose with senescence, treatments that delayed early senescence did not affect transcript abundance of WPS46, an auxin-induced gene. Conclusions A model for the interaction between cytokinins, ethylene, reactive oxygen species and auxin in the regulation of floral senescence in wallflowers is proposed. The combined increase in ethylene and reduction in cytokinin triggers the initiation of senescence and these two plant growth regulators directly or indirectly result in increased reactive oxygen species levels. A fall in conjugated auxin and/or the total auxin pool eventually triggers abscission.

What controls the vertical distribution of aerosol? Relationships between process sensitivity in HadGEM3–UKCA and inter-model variation from AeroCom Phase II

The vertical profile of aerosol is important for its radiative effects, but weakly constrained by observations on the global scale, and highly variable among different models. To investigate the controlling factors in one particular model, we investigate the effects of individual processes in HadGEM3–UKCA and compare the resulting diversity of aerosol vertical profiles with the inter-model diversity from the AeroCom Phase II control experiment. In this way we show that (in this model at least) the vertical profile is controlled by a relatively small number of processes, although these vary among aerosol components and particle sizes. We also show that sufficiently coarse variations in these processes can produce a similar diversity to that among different models in terms of the global-mean profile and, to a lesser extent, the zonal-mean vertical position. However, there are features of certain models' profiles that cannot be reproduced, suggesting the influence of further structural differences between models. In HadGEM3–UKCA, convective transport is found to be very important in controlling the vertical profile of all aerosol components by mass. In-cloud scavenging is very important for all except mineral dust. Growth by condensation is important for sulfate and carbonaceous aerosol (along with aqueous oxidation for the former and ageing by soluble material for the latter). The vertical extent of biomass-burning emissions into the free troposphere is also important for the profile of carbonaceous aerosol. Boundary-layer mixing plays a dominant role for sea salt and mineral dust, which are emitted only from the surface. Dry deposition and below-cloud scavenging are important for the profile of mineral dust only. In this model, the microphysical processes of nucleation, condensation and coagulation dominate the vertical profile of the smallest particles by number (e.g. total CN  >  3 nm), while the profiles of larger particles (e.g. CN  >  100 nm) are controlled by the same processes as the component mass profiles, plus the size distribution of primary emissions. We also show that the processes that affect the AOD-normalised radiative forcing in the model are predominantly those that affect the vertical mass distribution, in particular convective transport, in-cloud scavenging, aqueous oxidation, ageing and the vertical extent of biomass-burning emissions.

Garlic (Allium sativum L.) and ready-to-eat garlic products: In vitro antioxidant activity

Garlic contains polyphenol and sulphur compounds, which are responsible for its antioxidant activity (AA). This study aimed at evaluating the AA of fresh garlic and its commercialised products and their shelf life. Fresh garlic (FG) and its products, i.e. chopped with salt (CGS), chopped without Salt (CG), fried (FRG) and mixed garlic (FG with dehydrated garlic; MG) antioxidant activity was evaluated by three different methods: DPPH (1,1-diphenyl-2-picrylhydrazyl) assay, beta-carotene/linoleic acid assay and Rancimat method. Amongst all the analysed products, fried garlic presented the highest antioxidant activity. The free radical-scavenging activity decreased during the shelf life of all analysed products that correlated with the decrease in the total polyphenol content. Our findings suggest that some compounds other than phenol may have contributed towards this outcome. (c) 2008 Elsevier Ltd. All rights reserved.

Extracts from pitanga (Eugenia uniflora L.) leaves: Influence of extraction process on antioxidant properties and yield of phenolic compounds

Different extraction processes were employed to extract the polyphenolic compounds from pitanga (Eugenia uniflora L) leaves: a one-step process using water, ethanol or supercritical CO(2) as solvents, and a two-step process using supercritical CO(2) followed by either water or ethanol. The total polyphenolic compounds, total flavonoids and antioxidant activity were determined in all the extracts obtained. The process performance was evaluated with respect to three variables: global extraction yield, concentration and yield of both polyphenols and flavonoids in the extracts. For the one-step extraction, the results showed that the extraction yield increased with solvent polarity. For the two-step process, the results suggested that water was more efficient in extracting the phenolic compounds from E. uniflora when the matrix was previously extracted with scCO(2). With respect to the antioxidant activity, the ethanolic extracts obtained from both processes, using either the DPPH radical scavenging method or the beta-carotene bleaching method, presented high antioxidant activities. (C) 2010 Elsevier B.V. All rights reserved.