CO and NO2 pollution in a long two-way traffic road tunnel: investigation of NO2/NOx ratio and modelling of NO2 concentration

The CO, NO and NO2 concentrations, visibility and air flow velocity were measured using continuous analysers in a long Norwegian road tunnel (7.5 km) with traffic in both directions in April 1994 and 1995. The traffic density was monitored at the same time. The NO2 concentration exceeded Norwegian air quality limits for road tunnels 17% of the time in 1994. The traffic through the tunnel decreased from 1994 to 1995, and the mean NO2 concentration was reduced from 0.73 to 0.22 ppm. The ventilation fan control, based on the CO concentration only, was unsatisfactory and the air flow was sometimes low for hours. Models for NO2 concentration based on CO concentration and absolute air flow velocity were developed and tested. The NO2/NOx ratio showed an increase for NOx levels above 2 ppm; a likely explanation for this phenomenon is NO oxidation by O2. Exposure to high NO2 concentrations may represent a health risk for people with respiratory and cardiac diseases. In long road tunnels with two-way traffic, this study indicates that ventilation fan control based on CO concentration should be adjusted for changes in vehicle CO emission and should be supplemented by air flow monitoring to limit the NO2 concentration.     

Partitioning of mercury onto suspended sediments in estuaries

Radiochemical partitioning experiments using 203Hg have been undertaken with mixtures of river, seawater and sediment samples taken from three geochemically contrasting UK estuaries: the Plym, Beaulieu and Mersey. Species of dissolved Hg were determined using reversed-phase C18 chelating columns and particulate species were determined by sequential leaching with 1 M NH4OAc and 1 M HCl. Mercury had a high particle reactivity with partition coefficients, KDs, ranging from 10(4) to 5 x 10(5) ml g(-1), depending on salinity, the chemical composition of the end-member waters, and on the physico-chemical characteristics of the sediment. Dissolved organic matter present in the waters (humic substances and/or anthropogenic compounds) was found to be the main factor governing the forms of dissolved Hg and their reactivity. From the spiked 203Hg, up to 95% of the dissolved metal was retained on the C18 columns for the Mersey waters, whereas this fraction was < 60% in the Plym and Beaulieu waters. Quasi-irreversible adsorption of Hg onto particles from each estuary was observed over a time-scale of a few hours and < 20% of total particulate Hg was released by the sequential leach. In this paper, physico-chemical processes are proposed to explain the estuarine behaviour of Hg and the results are discussed in terms of Hg availability in estuarine systems.     

Chemical monitoring and evaluation of the water quality of the Douro River at the Crestuma-Lever dam

Water taken from the Crestuma-Lever dam on the Douro River was evaluated considering the Portuguese Decree-law no. 236/98 of 1st August, 1998. This paper presents the metrological characteristics, validation of analytical methodologies and the data obtained from seasonal samplings. The test parameters selected are: temperature, pH, chloride, conductivity, carbon dioxide, alkalinity, hardness, oxidability, dissolved oxygen, BOD5, total suspended solids, sulfide, phosphate, silica, ammonium, nitrite, nitrate, sulfate, sodium, potassium, calcium, magnesium, iron, manganese, copper and zinc. From data analysis we can conclude that the water presented the following characteristics: a pH situated in the neutral zone; a median mineralization; a medium hardness; well oxygenated water; and a carbonate hardness exclusively due to bicarbonates. The temperature, pH, dissolved oxygen, ammonia, chlorides, sulfates, copper, zinc and BOD5 were compared with the legal limits presented in annexes XXI and I of Decree-law 236/98. The results relating to total hardness, nitrites, calcium, magnesium, sodium, potassium, aluminium, sulfides and oxidability were compared with the legal values in annex VI as there are no limits relating to these parameters in annexes XXI and I.     

Assessing land use impacts on flood processes in complex terrain by using GIS and modeling approach

A distributed hydrologic modeling and GIS approach is applied for the assessment of land use impact in the Steinsel sub-basin, Alzette, Grand-Duchy of Luxembourg. The assessment focuses on the runoff contributions from different land use classes and the potential impact of land use changes on runoff generation. The results show that the direct runoff from urban areas is dominant for a flood event compared with runoff from other land use areas in this catchment, and tends to increase for small floods and for the dry season floods, whereas the interflow from forested, pasture and agricultural field areas contributes to the recession flow. Significant variations in flood volume, peak discharge, time to the peak, etc., are found from the model simulation based on the three hypothetical land use change scenarios.     

Application of a checklist for quality assistance in environmental modelling to an energy model

Large, complex energy models present considerable challenges to develop and test. Uncertainty assessments of such models provide only partial guidance on the quality of the results. We have developed a model quality assistance checklist to aid in this purpose. The model checklist provides diagnostic output in the form of a set of pitfalls for the model application. The checklist is applied here to an energy model for the problem of assessing energy use and greenhouse gas emissions. Use of the checklist suggests that results on this issue are contingent on a number of assumptions that are highly value-laden. When these assumptions are held fixed, the model is deemed capable of producing moderately robust results of relevance to climate policy over the longer term. Checklist responses also indicate that a number of details critical to policy choices or outcomes on this issue are not captured in the model, and model results should therefore be supplemented with alternative analyses.     

Assessment of the Heavy Metal Pollution Effects on the Soil Respiration in the Baix Llobregat (Catalonia, NE Spain)

A main goal of investigations is to determine could a soilrespiration be an indicator of the soil pollution. In this case a measured levelof the soil oxygen consumption depends of its pollution. It alsomeans that the pollution reduces biological processes in edaphon.Investigated soil samples were taken from polluted andnon-polluted places in the Baix Llobregat near Barcelona (Catalonia, NE Spain). Soil samples were taken from the top ofsoil (0–5 cm) without a litter. Soil analysis were done, determining percentage shares of coarsefragments, coarse sand, fine sand, coarse silt, fine silt, clay,CaCO₃, organic matter as well as water pH and conductivityCE (1:5 [mS cm^-1]). Also were determined (in mg kg^-1)quantities of heavy metals, as Fe, Al, Mn, Zn, Cr, Ni, V, Cu, Cd, Pb.The soil respiration was investigated in temperatures15 and 30 °C and with controlled humidity.The respiration in 30 °C is number of times greater thenin 15 °C both for polluted and non-polluted soils.Particularly high coefficients of correlation between the soilrespiration and soil pollution in polluted soils were obtainedfor Pb: r = 0.75 in 15 °C and r = 0.98 in30 °C; for Ba: 0.90 and 0.57; for V: 0.99 and 0.81. In non-polluted soils highest correlation coefficients are for Pb: r = 0.70 in 15 °C; Fe: 0.60 and 0.72; Al: 0.68 and0.64; Mn: 0.51 and 0.66; Ba: 0.63 and 0.61; Cr: 0.94 and0.70; Ni: 0.64 and 0.65; Cu: 0.69 and 0.48; as well as V: 0.62in 15 °C; and Cd: 0.69 in 15 °C.This way the soil respiration could be a good indicator of the soil pollution.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

A study of the distribution of lead, cadmium and copper between water and kaolin, bentonite and a river sediment

Experiments were carried out to monitor the equilibrium distribution of lead, cadmium and copper between an aqueous phase modelling natural water and a solid phase modelling natural sediment, under varying conditions. The aqueous phase was analysed using ETAAS and differential pulse anodic stripping voltammetry (DPASV), whereas XRD and FTIR were used to study the solid phase. Sorption isotherms at constant pH were measured. Conditional distribution constants were calculated as functions of the pH, the time of equilibration and the amount of solid material. The results obtained stress the need for standardization of the approaches to the study of water-sediment interactions in order to be able to evaluate and compare the extensive data from field measurements and to predict these interactions.