Local-scale fluxes of carbon dioxide in urban environments: methodological challenges and results from Chicago

Much attention is being directed to the measurement and modeling of surface-atmosphere exchanges of CO2 for different surface types. However, as yet, few measurements have been conducted in cities, even though these environments are widely acknowledged to be major sources of anthropogenic CO2. This paper highlights some of the challenges facing micrometeorologists attempting to use eddy covariance techniques to directly monitor CO2 fluxes in urban environments, focusing on the inherent variability within and between urban areas, and the importance of scale and the appropriate height of measurements. Results from a very short-term study of CO2 fluxes, undertaken in Chicago, Illinois in the summer of 1995, are presented. Mid-afternoon minimum CO2 concentrations and negative fluxes are attributed to the strength of biospheric photosynthesis and strong mixing of local anthropogenic sources in a deep mixed layer. Poor night-time atmospheric mixing, lower mixed layer depths, biospheric respiration, and continued missions from mobile and fixed anthropogenic sources, account for the night-time maxima in CO2 concentrations. The need for more, longer-term, continuous eddy covariance measurements is stressed.     

Insights into aqueous carbofuran removal by modified and non-modified rice husk biochars

Biochar has been considered as a potential sorbent for removal of frequently detected pesticides in water. In the present study, modified and non-modified rice husk biochars were used for aqueous carbofuran removal. Rice husk biochars were produced at 300, 500, and 700 °C in slow pyrolysis and further exposed to steam activation. Biochars were physicochemically characterized using proximate, ultimate, FTIR methods and used to examine equilibrium and dynamic adsorption of carbofuran. Increasing pyrolysis temperature led to a decrease of biochar yield and increase of porosity, surface area, and adsorption capacities which were further enhanced by steam activation. Carbofuran adsorption was pH-dependant, and the maximum (161 mg g^?1) occurred in the vicinity of pH 5, on steam-activated biochar produced at 700 °C. Freundlich model best fitted the sorption equilibrium data. Both chemisorption and physisorption interactions on heterogeneous adsorbent surface may involve in carbofuran adsorption. Langmuir kinetics could be applied to describe carbofuran adsorption in a fixed bed. A higher carbofuran volume was treated in a column bed by a steam-activated biochar versus non-activated biochars. Overall, steam-activated rice husk biochar can be highlighted as a promising low-cost sustainable material for aqueous carbofuran removal.     

Effects of clearfelling on stream and soil water aluminium chemistry in three UK forests

Data are presented demonstrating how clearfelling has changed soil and stream water aluminium chemistry. For soil waters, a strong empirical relationship was observed between inorganic aluminium (Al(inorg)) and total inorganic anion (TIA) concentrations. Before felling, chloride and sulphate accounted for the largest proportion of the TIA concentration. After felling, in soils where nitrification was active, nitrate became increasingly important. Where this led to an increase in TIA, Al(inorg) concentrations increased. Over five years, nitrate concentrations have fallen, along with TIA, resulting in a sympathetic decline in Al(inorg). Streams draining clearfelled areas initially became more acid, although chloride and sulphate concentrations decreased. Stream water nitrate concentrations increased soon after felling and remained higher than controls for up to four years. While nitrate concentrations were high, Al(inorg) remained unchanged. Subsequently, as nitrate and TIA decreased, Al(inorg) also declined to concentrations below those in the control stream. Clearfelling upland forests will not necessarily result in immediate improvements in water quality, although long-term benefits may be seen before canopy-closure of the next crop.     

Contribution of canopy leaching to sulphate deposition in a Scots pine forest

Radioactive sulphate (35SO4) was applied to the soil below a Scots pine forest on 23 June 1989, and its movement into the canopy and into throughfall and stemflow was measured over 4 months. The specific activity, Bq (mg S)(-1), of the canopy increased monotonically; uptake by current-year (1989) expanding needles was initially twice as fast as by older needles or live twigs. By 10 October the canopy average specific activity was 62 Bq (mg S)(-1). The specific activity of net throughfall (throughfall + stemflow - rain), deduced from measurements from six throughfall collectors, six stemflow collectors and two rain collectors, fell rapidly from 12.6 Bq (mg S)(-1) in late July to <1 Bq (mg S)(-1) in mid-August. The results suggest (assuming rapid equilibration of 35S with sulphate in soil) that root-derived sulphate contributed c. 3% of sulphate in net throughfall and that dry deposition of SO2 and sulphate particles contributed c. 97% of the 0.56 g S m(-2) measured in net throughfall over the period. Simultaneous measurements of SO2 at canopy height and of NH3 above and within the canopy gave mean concentrations of 5.9 and 0.86 microg m(-3), respectively, sufficient to account for the sulphate measured in net throughfall only if codeposition of NH3 and SO2 occurred to canopy surfaces. The large values of specific activity observed in July, however, indicate that throughfall composition may be closely related to recent soil input of sulphate, and that equilibrium cannot be safely assumed. The possibility of a significant contribution of soil-derived sulphate to sulphate deposition in net throughfall cannot be ruled out on the basis of this experiment.     

Cadmium availability to the cyanobacterium Synechocystis aquatilis in solutions containing chloride

Availability of cadmium to Synechocystis aquatilis (estimated by 109Cd sorption and cadmium toxicity-14C method) in solutions containing cadmium and complexing (KCl) or non-complexing (KNO3) salts, in the range of 0-0.5 m was investigated. Both cadmium surface adsorption and transport into the cells were lower in solutions containing cadmium chloride complexes (CdCl+, CdCl2, CdCl3-) than in those containing cadmium in the form of Cd2+. Also, cadmium toxicity in solutions of higher KCl concentrations, in which CdCl+ and CdCl2 forms predominated, was significantly limited.     

Seasonal trend of fog water chemical composition in the Po Valley

Fog frequency in the Po Valley, Northern Italy, can be as high as 30% of the time in the fall-winter season. High pollutant concentrations have been measured in fog water samples collected in this area over the past few years. The combined effects of high fog occurrence and high pollutant loading of the fog droplets can determine, in this area, appreciable chemical deposition rates. An automated station for fog water collection was developed, and deployed at the field station of S. Pietro Capofiume, in the eastern part of the Po Valley for an extended period: from the beginning of November 1989 to the end of April 1990. Time-resolved sampling of fog droplets was carried out during all fog events occurring in this period, and chemical analyses were performed on the collected samples. Statistical information on fog occurrence and fog water chemical composition is reported in this paper, and a tentative seasonal deposition budget is calculated for H+, NH4+, NO3- and SO4(2-) ions. The problems connected with fog droplet sampling in sub-freezing conditions are also addressed in the paper.     

Responses of microbial populations in the rhizosphere to deposition of simulated acidic rain onto foliage and/or soil

Air pollutants or some chemicals applied to plant foliage can alter the ecology of the rhizosphere. Experiments were conducted to distinguish among possible foliage-mediated versus soil- or root-mediated effects of acid deposition on microorganism in the rhizosphere. Seedlings of a sorghum x sudangrass hybrid in pots of non-sterile soil-sand mix in a greenhouse were exposed to simulated rain solution adjusted with H2SO4 + HNO3 to pH 4.9, 4.2, 3.5 or 2.8. Solutions were applied as simulated rain to foliage and soil, foliage only (soil covered by plastic, and deionized water applied directly to the soil), or soil only (solution applied directly to the soil). Solutions were applied on 16 days during a 6-week period (1.5 cm deposition in 1 h per application). Plant shoot and root dry weights and population densities of selected types of bacteria, filamentous actinomycetes and fungi in the rhizosphere were quantified after exposures were completed. Deposition of simulated acidic rain onto foliage alone had no effect on plant biomass or microbial population densities in the rhizosphere (colony-forming units per gram of rhizosphere soil). However, plant growth was stimulated and all microbial populations in the rhizosphere increased 3- to 8-fold with increased solution acidity (relative to pH 4.9 solution) when solution penetrated the soil. Statistical analyses indicated that the acid dose-population response relationships for soil-only and foliage-and-soil applications were not different. Thus, no foliage-mediated effect of simulated acidic rain on rhizosphere ecology was detected.     

Effects of atmospheric ammonia and ammonium sulphate on Douglas fir (Pseudotsuga menziesii)

Three-year-old Douglas firs (Pseudotsuga menziesii) were fumigated with 180 microg m(-3) NH3 or clean (charcoal-filtered) air. During these fumigations the plants received 15 mm artificial rain weekly, supplemented with 20, 500 or 2500 micromol litre(-1) (NH4)2SO4. Exposure to NH3 and NH4+ for 14 weeks resulted in a change of the nutrient status of the needles. The most remarkable effect was the increase in the N/K ratio, due to both uptake of N and leaching of K. The action of NH3 was stronger than that of NH4+. Both NH3 and (NH4)2SO4 affected the epicuticular wax layer and decreased mycorhiza frequency. Following fumigation and artificial rain treatments, needles were incubated for 8 h in a medium containing 0, 50, 250, 500 and 2500 micromol litre(-1) (NH4)2SO4. Almost no exchange of Ca, Mg and K for NH4+ was found. Therefore this ion exchange probably explains only a minor part of the changes in nutrient status of the whole trees.     

Real-world vehicle emissions: a summary of the tenth coordinating research council on-road vehicle emissions workshop

The Coordinating Research Council (CRC) held its tenth workshop in March 2000, focusing on results from the most recent real-world vehicle emissions research. In this paper, we summarize the presentations from researchers who are engaged in improving our understanding of the contribution of mobile sources to emission inventories. Participants in the workshop discussed efforts to improve mobile source emission models and emission inventories, results from gas- and particle-phase emissions studies from spark-ignition and diesel-powered vehicles, new methods for measuring mobile source emissions, improvements in vehicle emission control systems (ECSs), and evaluation of motor vehicle inspection/maintenance (I/M) programs, as well as topics for future research.     

Effects of thiobencarb herbicide to an alga (Nannochloris oculata) and the cladoceran (Daphnia magna)

Chronic toxicity studies were conducted with an algae (Nannochloris oculata) and the cladoceran (Daphnia magna) to determine their relative sensitivities to the thiocarbamate herbicide thiobencarb (S-4-chlorobenzyl diethylthiocarbamate). Most of the algal populations were initially affected by exposure to the herbicide. Thiobencarb concentrations higher than 0.5 mg/L significantly reduced algal densities after 24-h exposure. The 24-h static EC50 in D. magna was 3.01 mg/L. The sublethal effects of 0.3, 0.37, 0.5, 0.75, and 1.5 mg/L of thiobencarb concentrations on the survival, reproduction, and growth of D. magna were monitored for 21 days. The parameters used to determined the effect of the herbicide on D. magna were mean total young per female; mean brood size; days to first brood; intrinsic rate of natural increase (r); growth; and survival. Reproduction was significantly reduced at thiobencarb concentrations of 0.30 mg/L and higher while survival was affected after exposure to 0.75 and 1.5 mg/L of the pesticide. The r value decreased with increasing concentrations of thiobencarb. Growth, as measured by body length, was depressed significantly after exposure to all herbicide concentrations tested.