Over-parameterised, uncertain 'mathematical marionettes' - How can we best use catchment water quality models? An example of an 80-year catchment-scale nutrient balance

The Integrated Catchment Model of Nitrogen (INCA-N) was applied to the River Lambourn, a Chalk river-system in southern England. The model's abilities to simulate the long-term trend and seasonal patterns in observed stream water nitrate concentrations from 1920 to 2003 were tested. This is the first time a semi-distributed, daily time-step model has been applied to simulate such a long time period and then used to calculate detailed catchment nutrient budgets which span the conversion of pasture to arable during the late 1930s and 1940s. Thus, this work goes beyond source apportionment and looks to demonstrate how such simulations can be used to assess the state of the catchment and develop an understanding of system behaviour. The mass-balance results from 1921, 1922, 1991, 2001 and 2002 are presented and those for 1991 are compared to other modelled and literature values of loads associated with nitrogen soil processes and export. The variations highlighted the problem of comparing modelled fluxes with point measurements but proved useful for identifying the most poorly understood inputs and processes thereby providing an assessment of input data and model structural uncertainty. The modelled terrestrial and instream mass-balances also highlight the importance of the hydrological conditions in pollutant transport. Between 1922 and 2002, increased inputs of nitrogen from fertiliser, livestock and deposition have altered the nitrogen balance with a shift from possible reduction in soil fertility but little environmental impact in 1922, to a situation of nitrogen accumulation in the soil, groundwater and instream biota in 2002. In 1922 and 2002 it was estimated that approximately 2 and 18 kg N ha(-1) yr(-1) respectively were exported from the land to the stream. The utility of the approach and further considerations for the best use of models are discussed. (C) 2008 Elsevier B.V. All rights reserved.

Hydrochemical variations and contaminant load in the Rio Tinto (Spain) during flood events

The aim of this work is to study the hydrochemical variations during flood events in the Rio Tinto, SW Spain. Three separate rainfall/flood events were monitored in October 2004 following the dry season. In general, concentrations markedly increased following the first event (Fe from 99 to 1130 mg/L; Q(max) = 0.78 m(3)/s) while dissolved loads peaked in the second event (Fe = 7.5 kg/s, Cu = 0.83 kg/s, Zn = 0.82 kg/s; Q(max) = 77 m(3)/s) and discharge in the third event (Q(max) = 127 m(3)/s). This pattern reflects a progressive depletion of metals and sulphate stored in the dry summer as soluble evaporitic salt minerals and concentrated pore fluids, with dilution by freshwater becoming increasingly dominant as the month progressed. Variations in relative concentrations were attributed to oxyhydroxysulphate Fe precipitation, to relative changes in the sources of acid mine drainage (e.g. salt minerals, mine tunnels, spoil heaps etc.) and to differences in the rainfall distributions along the catchment. The contaminant load carried by the river during October 2004 was enormous, totalling some 770 t of Fe, 420 t of Al, 100 t of Cu, 100 t of Zn and 71 t of Mn. This represents the largest recorded example of this flush-out process in an acid mine drainage setting. Approximately 1000 times more water and 1408 200 times more dissolved elements were carried by the river during October 2004 than during the dry, low-flow conditions of September 2004, highlighting the key role of flood Events in the annual pollutant transport budget of semi-arid and and systems and the need to monitor these events in detail in order to accurately quantify pollutant transport. (c) 2007 Elsevier B.V. All rights reserved.

Over-parameterised, uncertain 'mathematical marionettes' - How can we best use catchment water quality models? An example of an 80-year catchment-scale nutrient balance

The Integrated Catchment Model of Nitrogen (INCA-N) was applied to the River Lambourn, a Chalk river-system in southern England. The model's abilities to simulate the long-term trend and seasonal patterns in observed stream water nitrate concentrations from 1920 to 2003 were tested. This is the first time a semi-distributed, daily time-step model has been applied to simulate such a long time period and then used to calculate detailed catchment nutrient budgets which span the conversion of pasture to arable during the late 1930s and 1940s. Thus, this work goes beyond source apportionment and looks to demonstrate how such simulations can be used to assess the state of the catchment and develop an understanding of system behaviour. The mass-balance results from 1921, 1922, 1991, 2001 and 2002 are presented and those for 1991 are compared to other modelled and literature values of loads associated with nitrogen soil processes and export. The variations highlighted the problem of comparing modelled fluxes with point measurements but proved useful for identifying the most poorly understood inputs and processes thereby providing an assessment of input data and model structural uncertainty. The modelled terrestrial and instream mass-balances also highlight the importance of the hydrological conditions in pollutant transport. Between 1922 and 2002, increased inputs of nitrogen from fertiliser, livestock and deposition have altered the nitrogen balance with a shift from possible reduction in soil fertility but little environmental impact in 1922, to a situation of nitrogen accumulation in the soil, groundwater and instream biota in 2002. In 1922 and 2002 it was estimated that approximately 2 and 18 kg N ha(-1) yr(-1) respectively were exported from the land to the stream. The utility of the approach and further considerations for the best use of models are discussed. (C) 2008 Elsevier B.V. All rights reserved.

Intake fraction of nonreactive motor vehicle exhaust in HongKong

The intake fraction (iF) of nonreactive constituents of exhaust from mobile vehicles in the urban area of HongKong is investigated using available monitoring data for carbon monoxide (CO) as a tracer of opportunity. Correcting for regional transport of carbon monoxide into HongKong, the annual-average iF for nonreactive motor vehicle emissions within the city is estimated to be around 270 per million. This estimated iF is much higher than values previously reported for vehicle emissions in US urban areas, Helsinki and Beijing, and somewhat lower than those reported for a densely populated street canyon in downtown Manhattan, New York City, or for emissions into indoor environments. The reported differences in intakefractions in various cities mainly result from the differences in local population densities. Our analysis highlights the importance of accounting for the influence of upwind transport of pollutants when using ambient data to estimate iF for an urban area. For vehicleexhaust in HongKong, it is found that the in/near vehicle microenvironment contributes similarly to the indoor home environment when accounting for the overall iF for children and adults. Keywords Intakefraction; Vehicle emission; Regional pollutant transport; Carbon monoxide; Exposure

PERSiST: a flexible rainfall-runoff modelling toolkit for use with the INCA family of models

Runoff generation processes and pathways vary widely between catchments. Credible simulations of solute and pollutant transport in surface waters are dependent on models which facilitate appropriate, catchment-specific representations of perceptual models of the runoff generation process. Here, we present a flexible, semi-distributed landscape-scale rainfall-runoff modelling toolkit suitable for simulating a broad range of user-specified perceptual models of runoff generation and stream flow occurring in different climatic regions and landscape types. PERSiST (the Precipitation, Evapotranspiration and Runoff Simulator for Solute Transport) is designed for simulating present-day hydrology; projecting possible future effects of climate or land use change on runoff and catchment water storage; and generating hydrologic inputs for the Integrated Catchments (INCA) family of models. PERSiST has limited data requirements and is calibrated using observed time series of precipitation, air temperature and runoff at one or more points in a river network. Here, we apply PERSiST to the river Thames in the UK and describe a Monte Carlo tool for model calibration, sensitivity and uncertainty analysis

Processes influencing ozone levels in Alaskan forest fire plumes during long-range transport over the North Atlantic

A case of long-range transport of a biomass burning plume from Alaska to Europe is analyzed using a Lagrangian approach. This plume was sampled several times in the free troposphere over North America, the North Atlantic and Europe by three different aircraft during the IGAC Lagrangian 2K4 experiment which was part of the ICARTT/ITOP measurement intensive in summer 2004. Measurements in the plume showed enhanced values of CO, VOCs and NOy, mainly in form of PAN. Observed O3 levels increased by 17 ppbv over 5 days. A photochemical trajectory model, CiTTyCAT, was used to examine processes responsible for the chemical evolution of the plume. The model was initialized with upwind data and compared with downwind measurements. The influence of high aerosol loading on photolysis rates in the plume was investigated using in situ aerosol measurements in the plume and lidar retrievals of optical depth as input into a photolysis code (Fast-J), run in the model. Significant impacts on photochemistry are found with a decrease of 18% in O3 production and 24% in O3 destruction over 5 days when including aerosols. The plume is found to be chemically active with large O3 increases attributed primarily to PAN decomposition during descent of the plume toward Europe. The predicted O3 changes are very dependent on temperature changes during transport and also on water vapor levels in the lower troposphere which can lead to O3 destruction. Simulation of mixing/dilution was necessary to reproduce observed pollutant levels in the plume. Mixing was simulated using background concentrations from measurements in air masses in close proximity to the plume, and mixing timescales (averaging 6.25 days) were derived from CO changes. Observed and simulated O3/CO correlations in the plume were also compared in order to evaluate the photochemistry in the model. Observed slopes change from negative to positive over 5 days. This change, which can be attributed largely to photochemistry, is well reproduced by multiple model runs even if slope values are slightly underestimated suggesting a small underestimation in modeled photochemical O3 production. The possible impact of this biomass burning plume on O3 levels in the European boundary layer was also examined by running the model for a further 5 days and comparing with data collected at surface sites, such as Jungfraujoch, which showed small O3 increases and elevated CO levels. The model predicts significant changes in O3 over the entire 10 day period due to photochemistry but the signal is largely lost because of the effects of dilution. However, measurements in several other BB plumes over Europe show that O3 impact of Alaskan fires can be potentially significant over Europe.

Cross-hemispheric transport of Central African biomass burning pollutants: Implications for downwind ozone production

Pollutant plumes with enhanced concentrations of trace gases and aerosols were observed over the southern coast of West Africa during August 2006 as part of the AMMA wet season field campaign. Plumes were observed both in the mid and upper troposphere. In this study we examined the origin of these pollutant plumes, and their potential to photochemically produce ozone (O3) downwind over the Atlantic Ocean. Their possible contribution to the Atlantic O3 maximum is also discussed. Runs using the BOLAM mesoscale model including biomass burning carbon monoxide (CO) tracers were used to confirm an origin from central African biomass burning fires. The plumes measured in the mid troposphere (MT) had significantly higher pollutant concentrations over West Africa compared to the upper tropospheric (UT) plume. The mesoscale model reproduces these differences and the two different pathways for the plumes at different altitudes: transport to the north-east of the fire region, moist convective uplift and transport to West Africa for the upper tropospheric plume versus north-west transport over the Gulf of Guinea for the mid-tropospheric plume. Lower concentrations in the upper troposphere are mainly due to enhanced mixing during upward transport. Model simulations suggest that MT and UT plumes are 16 and 14 days old respectively when measured over West Africa. The ratio of tracer concentrations at 600 hPa and 250 hPa was estimated for 14–15 August in the region of the observed plumes and compares well with the same ratio derived from observed carbon dioxide (CO2) enhancements in both plumes. It is estimated that, for the period 1–15 August, the ratio of Biomass Burning (BB) tracer concentration transported in the UT to the ones transported in the MT is 0.6 over West Africa and the equatorial South Atlantic. Runs using a photochemical trajectory model, CiTTyCAT, initialized with the observations, were used to estimate in-situ net photochemical O3 production rates in these plumes during transport downwind of West Africa. The mid-troposphere plume spreads over altitude between 1.5 and 6 km over the Atlantic Ocean. Even though the plume was old, it was still very photochemically active (mean net O3 production rates over 10 days of 2.6 ppbv/day and up to 7 ppbv/day during the first days) above 3 km especially during the first few days of transport westward. It is also shown that the impact of high aerosol loads in the MT plume on photolysis rates serves to delay the peak in modelled O3 concentrations. These results suggest that a significant fraction of enhanced O3 in mid-troposphere over the Atlantic comes from BB sources during the summer monsoon period. According to simulated occurrence of such transport, BB may be the main source for O3 enhancement in the equatorial south Atlantic MT, at least in August 2006. The upper tropospheric plume was also still photochemically active, although mean net O3 production rates were slower (1.3 ppbv/day). The results suggest that, whilst the transport of BB pollutants to the UT is variable (as shown by the mesoscale model simulations), pollution from biomass burning can make an important contribution to additional photochemical production of O3 in addition to other important sources such as nitrogen oxides (NOx) from lightning.