Link between DOC in near surface peat and stream water in an upland catchment

Hydrologic transport of dissolved organic carbon (DOC) from peat soils may differ to organo-mineral soils in how they responded to changes in flow, because of differences in soil profile and hydrology. In well-drained organo-mineral soils, low flow is through the lower mineral layer where DOC is absorbed and high flow is through the upper organic layer where DOC is produced. DOC concentrations in streams draining organo-mineral soils typically increase with flow. In saturated peat soils, both high and low flows are through an organic layer where DOC is produced. Therefore, DOC in stream water draining peat may not increase in response to changes in flow as there is no switch in flow path between a mineral and organic layer. To verify this, we conducted a high-resolution monitoring study of soil and stream water at an upland peat catchment in northern England. Our data showed a strong positive correlation between DOC concentrations at − 1 and − 5 cm depth and stream water, and weaker correlations between concentrations at − 20 to − 50 cm depth and stream water. Although near surface organic material appears to be the key source of stream water DOC in both peat and organo-mineral soils, we observed a negative correlation between stream flow and DOC concentrations instead of a positive correlation as DOC released from organic layers during low and high flow was diluted by rainfall. The differences in DOC transport processes between peat and organo-mineral soils have different implications for our understanding of long-term changes in DOC exports. While increased rainfall may cause an increase in DOC flux from peat due to an increase in water volume, it may cause a decrease in concentrations. This response is contrary to expected changes in DOC exports from organo-mineral soils, where increase rainfall is likely to result in an increase in flux and concentration.

Moisture transport in mid-latitude cyclones

We discuss how synoptic-scale variability controls the transport of atmospheric water vapour by mid-latitude cyclones. Idealised simulations are used to investigate quantitatively what factors determine the magnitude of cyclone moisture transport. It is demonstrated that large-scale ascent on the warmconveyor belt and shallow cumulus convection are equally important for ventilating moisture from the boundary layer into the free troposphere, and that ventilated moisture can be transported large distances eastwards and polewards by the cyclone, before being returned to the surface as precipitation. The initial relative humidity is shown to have little affect on the ability of the cyclone to transport moisture, whilst the absolute temperature and meridional temperature gradient provide much stronger controls. Scaling arguments are presented to quantify the dependence of moisture transport on large-scale and boundary-layer parameters. It is shown that ventilation by shallow convection and warm-conveyor belt advection vary in the same way with changes to large-scale parameters. However, shallow convective ventilation has a much stronger dependence on boundary-layer parameters than warm-conveyor belt ventilation.

Changes in water vapor transports of the ascending branch of the tropical circulation

Recent studies have found contradicting results on whether tropical atmospheric circulation (TAC) has intensified or weakened in recent decades. We here re-investigate recent changes in TAC derived from moisture transports into the tropics using high temporal and spatial resolution reanalyses from ERA-interim. We found a significant strengthening of both, the lower level inward transports and the mid level outward transports over the recent two decades. However the signal in the total budget is weak, because strengthening of the in and outflow neutralize each other, at least to some extent. We found atmospheric humidity to be relatively stable, so suggest that the intensification is mainly caused by an intensification of the wind related circulation strength. The exact quantitative values were found to heavily depend on whether the calculations are based on mean or instantaneous values. We highlight the importance for using the instantaneous ones for transport calculations, as they represent the coincidence of high wind speeds and high atmospheric humidity.

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modelled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmo- spheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270 K is close to unity. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for eðcient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

Upper-ocean heat budget and ocean eddy transport in the south-east Pacific in a high-resolution coupled model

We present an analysis of the oceanic heat advection and its variability in the upper 500 m in the southeastern tropical Pacific (100W–75W, 25S–10S) as simulated by the global coupled model HiGEM, which has one of the highest resolutions currently used in long-term integrations. The simulated climatology represents a temperature advection field arising from transient small-scale (<450 km) features, with structures and transport that appear consistent with estimates based on available observational data for the mooring at 20S, 85W. The transient structures are very persistent (>4 months), and in specific locations they generate an important contribution to the local upper-ocean heat budget, characterised by scales of a few hundred kilometres, and periods of over a year. The contribution from such structures to the local, long-term oceanic heat budget however can be of either sign, or vanishing, depending on the location; and, although there appears some organisation in preferential areas of activity, the average over the entire region is small. While several different mechanisms may be responsible for the temperature advection by transients, we find that a significant, and possibly dominant, component is associated with vortices embedded in the large-scale, climatological salinity gradient associated with the fresh intrusion of mid-latitude intermediate water which penetrates north-westward beneath the tropical thermocline

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KMGAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KMGAP is based on the PRA model framework (P¨oschl-Rudich- Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270K is close to unity (Winkler et al., 2006). Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

High prevalence of multidrug-tolerant bacteria and associated antimicrobial resistance genes isolated from ornamental fish and their carriage water

Background: Antimicrobials are used to directly control bacterial infections in pet (ornamental) fish and are routinely added to the water these fish are shipped in to suppress the growth of potential pathogens during transport. Methodology/Principal Findings: To assess the potential effects of this sustained selection pressure, 127 Aeromonas spp. isolated from warm and cold water ornamental fish species were screened for tolerance to 34 antimicrobials. Representative isolates were also examined for the presence of 54 resistance genes by a combination of miniaturized microarray and conventional PCR. Forty-seven of 94 Aeromonas spp. isolates recovered from tropical ornamental fish and their carriage water were tolerant to >= 15 antibiotics, representing seven or more different classes of antimicrobial. The quinolone and fluoroquinolone resistance gene, qnrS2, was detected at high frequency (37% tested recent isolates were positive by PCR). Class 1 integrons, IncA/C broad host range plasmids and a range of other antibiotic resistance genes, including floR, blaTEM21, tet(A), tet(D), tet(E), qacE2, sul1, and a number of different dihydrofolate reductase and aminoglycoside transferase coding genes were also detected in carriage water samples and bacterial isolates. Conclusions: These data suggest that ornamental fish and their carriage water act as a reservoir for both multi-resistant bacteria and resistance genes.

The influence of eddy parameterizations on the transport of the Antarctic Circumpolar Current in coupled climate models

The transport of the Antarctic Circumpolar Current (ACC) varies strongly across the coupled GCMs (general circulation models) used for the IPCC AR4. This note shows that a large fraction of this across-model variance can be explained by relating it to the parameterization of eddy-induced transports. In the majority of models this parameterization is based on the study by Gent and McWilliams (1990). The main parameter is the quasi-Stokes diffusivity kappa (often referred to less accurately as ’’thickness diffusion’’). The ACC transport and the meridional density gradient both correlate strongly with kappa across those models where kappa is a prescribed constant. In contrast, there is no correlation with the isopycnal diffusivity jiso across the models. The sensitivity of the ACC transport to kappa is larger than to the zonal wind stress maximum. Experiments with the fast GCM FAMOUS show that changing kappa directly affects the ACC transport by changing the density structure throughout the water column. Our results suggest that this limits the role of the wind stress magnitude in setting the ACC transport in FAMOUS. The sensitivities of the ACC and the meridional density gradient are very similar across the AR4 GCMs (for those models where kappa is a prescribed constant) and among the FAMOUS experiments. The strong sensitivity of the ACC transport to kappa needs careful assessment in climate models.

Water quality trends in the Windrush catchment: Nitrogen speciation and sediment interactions

For the predominantly agricultural River Windrush catchment, spatial variations in concentrations of nitrogen species and suspended sediment were strongly related to geology and land use. Temporal patterns of NO3- and NO2- concentrations during the three year study were highly correlated with seasonal variations in baseflow. Suspended sediment concentrations were mainly controlled by storm discharge. Variations in total ammonium concentrations reflected both flow controls. Suspended sediment effects total ammonium and organic nitrogen transport to the aquatic system, and in-stream cycling processes. Organic nitrogen did not display consistent seasonal variations, but concentrations occasionally exceeding those of NO3-. Overall, NO3- and organic nitrogen were the most important at 60% and -40%, of total nitrogen load, respectively. Future assessments of agriculture impact on river water quality should consider the total nitrogen load, and not solely that of NO3-.

Potential role of the quasi-biennial oscillation in the stratosphere-troposphere exchange as found in water vapor in general circulation model experiments

The tropical tropopause is considered to be the main region of upward transport of tropospheric air carrying water vapor and other tracers to the tropical stratosphere. The lower tropical stratosphere is also the region where the quasi-biennial oscillation (QBO) in the zonal wind is observed. The QBO is positioned in the region where the upward transport of tropospheric tracers to the overworld takes place. Hence the QBO can in principle modulate these transports by its secondary meridional circulation. This modulation is investigated in this study by an analysis of general circulation model (GCM) experiments with an assimilated QBO. The experiments show, first, that the temperature signal of the QBO modifies the specific humidity in the air transported upward and, second, that the secondary meridional circulation modulates the velocity of the upward transport. Thus during the eastward phase of the QBO the upward moving air is moister and the upward velocity is less than during the westward phase of the QBO. It was further found that the QBO period is too short to allow an equilibration of the moisture in the QBO region. This causes a QBO signal of the moisture which is considerably smaller than what could be obtained in the limiting case of indefinitely long QBO phases. This also allows a high sensitivity of the mean moisture over a QBO cycle to the El Niño-Southern Oscillation (ENSO) phenomena or major tropical volcanic eruptions. The interplay of sporadic volcanic eruptions, ENSO, and QBO can produce low-frequency variability in the water vapor content of the tropical stratosphere, which renders the isolation of the QBO signal in observational data of water vapor in the equatorial lower stratosphere difficult.

Transport timescales and tracer properties in the extratropical UTLS

A comprehensive evaluation of seasonal backward trajectories initialized in the northern hemisphere lowermost stratosphere (LMS) has been performed to investigate the factors that determine the temporal and spatial structure of troposphere-to-stratosphere-transport (TST) and it's impact on the LMS. In particular we explain the fundamental role of the transit time since last TST (tTST) for the chemical composition of the LMS. According to our results the structure of the LMS can be characterized by a layer with tTST<40 days forming a narrow band around the local tropopause. This layer extends about 30 K above the local dynamical tropopause, corresponding to the extratropical tropopause transition layer (ExTL) as identified by CO. The LMS beyond this layer shows a relatively well defined separation as marked by an aprupt transition to longer tTST indicating less frequent mixing and a smaller fraction of tropospheric air. Thus the LMS constitutes a region of two well defined regimes of tropospheric influence. These can be characterized mainly by different transport times from the troposphere and different fractions of tropospheric air. Carbon monoxide (CO) mirrors this structure of tTST due to it's finite lifetime on the order of three months. Water vapour isopleths, on the other hand, do not uniquely indicate TST and are independent of tTST, but are determined by the Lagrangian Cold Point (LCP) of air parcels. Most of the backward trajectories from the LMS experienced their LCP in the tropics and sub-tropics, and TST often occurs 20 days after trajectories have encountered their LCP. Therefore, ExTL properties deduced from CO and H2O provide totally different informations on transport and particular TST for the LMS.

Freshwater transport in the coupled ocean-atmosphere system: a passive ocean

Conservation of water demands that meridional ocean and atmosphere freshwater transports (FWT) are of equal magnitude but opposite in direction. This suggests that the atmospheric FWT and its associated latent heat (LH) transport could be thought of as a \textquotedblleft coupled ocean/atmosphere mode\textquotedblright. But what is the true nature of this coupling? Is the ocean passive or active? Here we analyze a series of simulations with a coupled ocean-atmosphere-sea ice model employing highly idealized geometries but with markedly different coupled climates and patterns of ocean circulation. Exploiting streamfunctions in specific humidity coordinates for the atmosphere and salt coordinates for the ocean to represent FWT in their respective medium, we find that atmospheric FWT/LH transport is essentially independent of the ocean state. Ocean circulation and salinity distribution adjust to achieve a return freshwater pathway demanded of them by the atmosphere. So, although ocean and atmosphere FWTs are indeed coupled by mass conservation, the ocean is a passive component acting as a reservoir of freshwater.

Impact of the Arctic Ocean Atlantic water layer on Siberian shelf hydrography

This paper examines the role of the Arctic Ocean Atlantic water (AW) in modifying the Laptev Sea shelf bottom hydrography on the basis of historical records from 1932 to 2008, field observations carried out in April–May 2008, and 2002–2009 cross‐slope measurements. A climatology of bottom hydrography demonstrates warming that extends offshore from the 30–50 m depth contour. Bottom layer temperature‐time series constructed from historical records links the Laptev Sea outer shelf to the AW boundary current transporting warm and saline water from the North Atlantic. The AW warming of the mid‐1990s and the mid‐2000s is consistent with outer shelf bottom temperature variability. For April–May 2008 we observed on‐shelf near‐bottom warm and saline water intrusions up to the 20 m isobath. These intrusions are typically about 0.2°C warmer and 1–1.5 practical salinity units saltier than ambient water. The 2002–2009 cross‐slope observations are suggestive for the continental slope upward heat flux from the AW to the overlying low‐halocline water (LHW). The lateral on‐shelf wind‐driven transport of the LHW then results in the bottom layer thermohaline anomalies recorded over the Laptev Sea shelf. We also found that polynya‐induced vertical mixing may act as a drainage of the bottom layer, permitting a relatively small portion of the AW heat to be directly released to the atmosphere. Finally, we see no significant warming (up until now) over the Laptev Sea shelf deeper than 10–15 m in the historical record. Future climate change, however, may bring more intrusions of Atlantic‐modified waters with potentially warmer temperature onto the shelf, which could have a critical impact on the stability of offshore submarine permafrost.

Transit times – the link between hydrology and water quality at the catchment scale

In spite of trying to understand processes in the same spatial domain, the catchment hydrology and water quality scientific communities are relatively disconnected and so are their respective models. This is emphasized by an inadequate representation of transport processes, in both catchment-scale hydrological and water quality models. While many hydrological models at the catchment scale only account for pressure propagation and not for mass transfer, catchment scale water quality models are typically limited by overly simplistic representations of flow processes. With the objective of raising awareness for this issue and outlining potential ways forward we provide a non-technical overview of (1) the importance of hydrology-controlled transport through catchment systems as the link between hydrology and water quality; (2) the limitations of current generation catchment-scale hydrological and water quality models; (3) the concept of transit times as tools to quantify transport and (4) the benefits of transit time based formulations of solute transport for catchment-scale hydrological and water quality models. There is emerging evidence that an explicit formulation of transport processes, based on the concept of transit times has the potential to improve the understanding of the integrated system dynamics of catchments and to provide a stronger link between catchment-scale hydrological and water quality models.

Triple isotope (δD, δ17O, δ18O) study on precipitation, drip water and speleothem fluid inclusions for a central European cave (NW Switzerland)

Deuterium (dD) and oxygen (d18O) isotopes are powerful tracers of the hydrological cycle and have been extensively used for paleoclimate reconstructions as they can provide information on past precipitation, temperature and atmospheric circulation. More recently, the use of 17Oexcess derived from precise measurement of d17O and d18O gives new and additional insights in tracing the hydrological cycle whereas uncertainties surround this proxy. However, 17Oexcess could provide additional information on the atmospheric conditions at the moisture source as well as about fractionations associated with transport and site processes. In this paper we trace water stable isotopes (dD, d17O and d18O) along their path from precipitation to cave drip water and finally to speleothem fluid inclusions for Milandre cave in northwestern Switzerland. A two year-long daily resolved precipitation isotope record close to the cave site is compared to collected cave drip water (3 months average resolution) and fluid inclusions of modern and Holocene stalagmites. Amount weighted mean dD, d18O and d17O are �71.0‰, �9.9‰, �5.2‰ for precipitation, �60.3‰, �8.7‰, �4.6‰ for cave drip water and �61.3‰, �8.3‰, �4.7‰ for recent fluid inclusions respectively. Second order parameters have also been derived in precipitation and drip water and present similar values with 18 per meg for 17Oexcess whereas d-excess is 1.5‰ more negative in drip water. Furthermore, the atmospheric signal is shifted towards enriched values in the drip water and fluid inclusions (D of ~ þ 10‰ for dD). The isotopic composition of cave drip water exhibits a weak seasonal signal which is shifted by around 8e10 months (groundwater residence time) when compared to the precipitation. Moreover, we carried out the first d17O measurement in speleothem fluid inclusions, as well as the first comparison of the d17O behaviour from the meteoric water to the fluid inclusions entrapment in speleothems. This study on precipitation, drip water and fluid inclusions will be used as a speleothem proxy calibration for Milandre cave in order to reconstruct paleotemperatures and moisture source variations for Western Central Europe.