Nonlinearities in source receptor relationships for sulfur and nitrogen compounds

The relationship between emissions and deposition of air pollutants, both spatially and in time forms an important focus for science and for policy makers. In practice, this relationship may become nonlinear if the underlying processes change with time, or in space. Nonlinearities may also appear due to errors in emission or deposition data, and careful scrutiny of both data sources and their relationship provides a means of picking up such deficiencies. Nonlinearities in source receptor relationships for sulfur and nitrogen compounds in Europe have been identified in measurement data for the UK. In the case of sulfur, the dry deposition process has been shown to be strongly influenced by ambient concentrations of NH3, leading to substantial increases in deposition rate as SO2 concentrations decline and the ratio SO2/NH3 decreases. The field evidence extends to measurements over three different surfaces in three countries across Europe. A mechanistic understanding of the cause of this nonlinearity has been provided. Apparent nonlinearities also exist in the sulfur deposition field through the influence of shipping emissions. The effect is clear at west coast locations, where during a period in which land-based sulfur emissions declined by 50%, no significant decline in concentrations of SO(2-) in precipitation were observed. The sites affected are primarily the coastal regions of southwestern UK, where shipping sources contribute a substantial fraction of the deposited sulfur, but the effect is not detectable elsewhere. Full quantification of the spatially disaggregated emission and their changes in time will eliminate this apparent nonlinearity in the source-receptor data. For oxidized nitrogen emission and deposition in the UK, there is strong evidence of nonlinearity in the source-receptor relationship. The concentrations and deposition of NO(3-) in precipitation have declined little following a reduction in emissions of 45% during the period 1987 to 2001. The data imply a significant decrease in the average transport distance for oxidized nitrogen and most probably an increase in the average oxidation rate. However, the net effect of changes in aerosol chemistry due to changes in sulfur emissions and less competition for the main oxidants as a consequence of reductions in sulfur emission have not been separated. A quantitative explanation of the cause of this nonlinearity is lacking and the effects are therefore identified as an important uncertainty for the development of further protocols to control acidification, eutrophication and photochemical oxidants in Europe.     

Sensitivity of a forest ecosystem model to climate parametrization schemes

An analysis of the climate parametrization scheme adopted by conventional forest gap models revealed that most models assume a constant climate and are difficult to calibrate consistently. Tree growth showed unrealistically sensitive threshold effects along ecological gradients of temperature and precipitation. A new parametrization was compared with its predecessors in terms of the model's capability to predict realistic steady state species compositions at three test sites in the Alps. Applying the new model variant ForClim to some climate-change scenarios suggests that forest gap models are highly sensitive to climate pametrizations, regardless of the realism with which they simulate forests for the current climate. Moreover, the precision of climate scenarios based on General Circulation Models (GCM), for example, falls short of ForClim's sensitivity. Climate-dependent processes in forest gap models should be rehearsed before these models are used in impact studies of climatic change.     

Plasma ALP activity and blood PCV value changes in chick fetuses due to exposure of the egg to different xenobiotics

The effects of two polycyclic aromatic hydrocarbon (PAH) compounds (benz(k)fluoranthene and fluoranthene) and two heavy metals (cadmium and lead) were studied on the alkaline phosphatase (ALP) enzyme activity and hematocrit (PCV) values in chick fetuses. Eggs were exposed to one of the four compounds before incubation, by applying two exposure methods: injection (into the air cell) or immersion. Fluoranthene, cadmium and lead injection significantly decreased ALP activity compared to the control, while none of the compounds caused significant reduction in ALP activity in the immersion groups; however, a decreasing tendency was seen in these groups as well. Hematocrit values were increased after benz(k)fluoranthene immersion, fluoranthene immersion and cadmium injection. However, the doses in this study are relatively low (compared to other ecotoxicological studies in birds), the alteration in ALP enzyme activity and PCV values was apparent in each treatment group and is indicative of the high sensitivity of chick fetuses.     

Convergent-flow tracer tests in heterogeneous media: combined experimental-numerical analysis for determination of equivalent transport parameters

In modeling transport within naturally heterogeneous aquifers, it is usually assumed that the transport equations valid at local scales can also be applied at larger scales. At larger scales, the heterogeneous domain is represented by an equivalent homogeneous medium. Convergent-flow tracer tests constitute one of the most frequently used field tests to estimate effective input parameters of equivalent homogeneous aquifers. Traditionally, statistical approaches applied to groundwater flow and solute transport have provided tools to estimate these equivalent parameters. These approaches are based on a number of simplifications including the assumption that the point transmissivity values follow a multilog-normal random function. Several investigators have found that this assumption may not be valid in many field cases. In order to study the applicability of the equivalent homogeneous formulation in a nontraditional stochastic field, a number of experimental and numerical studies were conducted. The results are used to determine the apparent values of porosity and dispersivity that would be obtained if convergent-flow tracer tests were conducted in a deterministically generated heterogeneous transmissivity field displaying anisotropy in the correlation structure. It is shown that in this particular heterogeneous media, apparent porosity strongly depends on connectivity rather than on transmissivity. This dependence on connectivity questions the theoretical results obtained in continuum equivalent fields to estimate effective porosity.     

Coastal aquaculture development in eastern Africa and the Western Indian Ocean: prospects and problems for food security and local economies

This paper reviews the experience and status of coastal aquaculture of seaweeds, mollusks, fish and crustaceans in eastern Africa and the islands of the western Indian Ocean. In many respects, coastal aquaculture is still in its infancy in the region, and there is a pressing need to formulate development strategies aimed at improving the income and assuring the availability of affordable protein to coastal communities. This paper also draws from positive and negative experiences in other parts of the world. The requirements of feed and fry, and the conversion of mangroves are used to illustrate how some aquaculture activities constitute a net loss to global seafood production. The paper presents both general and specific sustainability guidelines based on the acknowledgement of aquaculture as an ecological process. It is concluded that without clear recognition of its dependence on natural ecosystems, the aquaculture industry is unlikely to develop to its full potential in the region.     

BETR North America: a regionally segmented multimedia contaminant fate model for North America

We present the Berkeley-Trent North American contaminant fate model (BETR North America), a regionally segmented multimedia contaminant fate model based on the fugacity concept. The model is built on a framework that links contaminant fate models of individual regions, and is generally applicable to large, spatially heterogeneous areas. The North American environment is modeled as 24 ecological regions, within each region contaminant fate is described using a 7 compartment multimedia fugacity model including a vertically segmented atmosphere, freshwater, freshwater sediment, soil, coastal water and vegetation compartments. Inter-regional transport of contaminants in the atmosphere, freshwater and coastal water is described using a database of hydrological and meteorological data compiled with Geographical Information Systems (GIS) techniques. Steady-state and dynamic solutions to the 168 mass balance equations that make up the linked model for North America are discussed, and an illustrative case study of toxaphene transport from the southern United States to the Great Lakes Basin is presented. Regionally segmented models such as BETR North America can provide a critical link between evaluative models of long-range transport potential and contaminant concentrations observed in remote regions. The continent-scale mass balance calculated by the model provides a sound basis for evaluating long-range transport potential of organic pollutants, and formulation of continent-scale management and regulatory strategies for chemicals.     

Decolorization of synthetic dyes by the Fenton reagent and the Cu/pyridine/H2O2 system

Representative azo, triphenylmethane, heterocyclic and polymeric synthetic dyes have been decolorized by two biological non-ezymatic systems, copper/pyridine/H2O2 and the Fenton reagent. With the former system, intensive decolorization measured after 1 h was obtained with phenol red (89%), tropaeolin 00 (58%), Evans blue (95%), eosin yellowish (84%), and Poly B-411 (92%). The rate of decolorization was not affected by pH in the range of 3-9 and increased with increasing temperature. The use of the radical scavengers thiourea and superoxide dismutase showed that hydroxyl radicals rather than superoxide anions are involved in the reaction. Omission of pyridine led to a substantial decrease in the extent of decolorization (20-50% decolorization). The use of organic peroxide instead of H2O2 resulted in slightly slower decolorization, similar values of decolorization being obtained only after a 2-h incubation. Decolorization of the dyes by the Fenton reagent was also very effective but slower than that obtained with the first system. Except for phenol red and eosin yellowish, (decolorization 8% and 52%, respectively) the dyes were decolorized up to 99% after 1-day incubation.     

Effects of land use data on dry deposition in a regional photochemical model for eastern Texas

Land use data are among the inputs used to determine dry deposition velocities for photochemical grid models such as the Comprehensive Air Quality Model with extensions (CAMx) that is currently used for attainment demonstrations and air quality planning by the state of Texas. The sensitivity of dry deposition and O3 mixing ratios to land use classification was investigated by comparing predictions based on default U.S. Geological Survey (USGS) land use data to predictions based on recently compiled land use data that were collected to improve biogenic emissions estimates. Dry deposition of O3 decreased throughout much of eastern Texas, especially in urban areas, with the new land use data. Predicted 1-hr averaged O3 mixing ratios with the new land use data were as much as 11 ppbv greater and 6 ppbv less than predictions based on USGS land use data during the late afternoon. In addition, the area with peak O3 mixing ratios in excess of 100 ppbv increased significantly in urban areas when deposition velocities were calculated based on the new land use data. Finally, more detailed data on land use within urban areas resulted in peak changes in O3 mixing ratios of approximately 2 ppbv. These results indicate the importance of establishing accurate, internally consistent land use data for photochemical modeling in urban areas in Texas. They also indicate the need for field validation of deposition rates in areas experiencing changing land use patterns, such as during urban reforestation programs or residential and commercial development.     

Methylmercury and total mercury in estuarine organisms from Rio de Janeiro, Brazil

Guanabara Bay (GB), located in the Rio de Janeiro State, is still a productive estuary on the south-eastern Brazilian coast. It is an ecosystem heavily impacted by organic matter, oil and a number of other toxic compounds, including Hg. The present study aimed to comparatively evaluate the aquatic total mercury (THg) and MeHg contamination, and the ratios of MeHg to THg (% MeHg), in 3 species of marine organisms, Micropogonias furnieri-carnivorous fish (N = 81), Mugil spp.--detritivorous fish (N = 20) and Perna perna--filter-feeding bivalves (N = 190), which are widely consumed by the population. A total of 291 specimens were collected at the bay in different periods between 1988 and 1998. THg concentrations were determined by cold vapour AAS with stannous chloride as a reducing agent. MeHg was extracted by dithizone-benzene and measured by GC-ECD. Analytical quality was checked through certified standards. All organisms presented both low THg and MeHg concentrations and they were below the maximum limit of 1,000 micrograms Hg.kg-1 wet wt. as established for human intake of predatory fish by the new Brazilian legislation. Carnivorous fish showed higher THg and MeHg concentrations, and also % MeHg in muscle tissues, than organisms with other feeding habits and lower trophic levels. The average of THg concentrations in carnivorous fish was 108.9 +/- 58.6 micrograms.kg-1 wet wt. (N = 61) in 1990 and 199.5 +/- 116.2 micrograms.kg-1 wet wt. (N = 20) in 1998, but they presented different total length and body weights. The average THg content in detritivorous fish was 15.4 +/- 5.8 micrograms.kg-1 wet wt., whereas THg concentrations ranged from 4.1 to 53.5 micrograms.kg-1 wet wt. for the molluscs. The THg and MeHg contents of mussel varied according to the sampling point and water quality. MeHg concentration in detritivorous fish was similar to MeHg concentration in molluscs, but there was a significant difference in the MeHg/THg ratio: the carnivorous fish presented higher MeHg percentages (98%) than the detritivorous fish (54%) and the molluscs (33%). Weight-normalised average concentration of THg in carnivorous fish collected in 1990 (0.18 +/- 0.08 microgram.g-1/0.7 kg wet wt.) and in 1998 (0.16 +/- 0.09 microgram.g-1/0.7 kg wet wt.) presented no significant difference (t = 1.34; P < 0.5). In conclusion, the low THg and MeHg concentrations in the organisms from the GB ecosystem, are related to its eutrophic conditions and elevated amounts of suspended matter. In this situation, Hg could be strongly complexed or adsorbed by the particulate, which would dilute the Hg inputs and reduce its residence time in the water column, with a consequent decrease in its availability to organisms.     

Windblown dust contributes to high PM2.5 concentrations

The revised National Ambient Air Quality Standards for PM include fine particulate standards based upon mass measurements of PM2.5. It is possible in arid and semi-arid regions to observe significant coarse mode intrusion in the PM2.5 measurement. In this work, continuous PM10, PM2.5, and PM1.0 were measured during several windblown dust events in Spokane, WA. PM2.5 constituted approximately 30% of the PM10 during the dust event days, compared with approximately 48% on the non-dusty days preceding the dust events. Both PM10 and PM2.5 were enhanced during the dust events. However, PM1.0 was not enhanced during dust storms that originated within the state of Washington. During a dust storm that originated in Asia and impacted Spokane, PM1.0 was also enhanced, although the Asian dust reached Washington during a period of stagnation and poor dispersion, so that local sources were also contributing to high particulate levels. The "intermodal" region of PM, defined as particles ranging in aerodynamic size from 1.0 to 2.5 microns, was found to represent a significant fraction of PM2.5 (approximately 51%) during windblown dust events, compared with 28% during the non-dusty days before the dust events.