The Impact of the Hyperacid Ijen Crater Lake. Part I: Concentrations of Elements in Crops and Soil

In Asembagus (East Java, Indonesia) irrigation water is contaminated with effluent from the hyperacid Ijen Crater Lake resulting in a low pH and high levels of various elements. As a first step towards a risk assessment, locally produced food items (rice, maize, cassava leaf, cassava root, peanuts) were collected and concentrations of As, B, Ca, Cd, Co, Cu, Fe, Mg, Mn, Mo, Ni, Pb, V, Zn were compared to samples from a reference area and with literature values. Further, concentrations in rice were compared to total soil concentrations in paddy fields. Compared to the reference area, food items produced in the contaminated area had increased levels of Cd, Co, Ni and Mn in particular, while levels of Mo were lower. In contrast, total soil concentrations of Cd and Mn in particular have decreased whereas especially Mo was increased. In combination with the observed soil acidification, it is likely that the bioavailable concentration of most elements in the contaminated soil is higher (except for Mo) due to an increased weathering rate and/or input via the contaminated irrigation water. In terms of human health, concentrations in foods were generally within normal literature values. However, it was observed that essential elements (in particular Fe) known for their inhibitory effects on e.g. Cd and Mn toxicity did not accumulate in crops whereas Cd and Mn did.     

Practical considerations for addressing uncertainties in monitoring bulk deposition

The assessment of the deposition of both wet (rain and cloud) and dry sedimenting particles is a prerequisite for estimating element fluxes in ecosystem research. Many nations and institutions operate deposition networks using different types of sampler. However, these samplers have rarely been characterized with respect to their sink properties. Major errors in assessing bulk deposition can result from poor sampling properties and defective sampling strategies. Relevant properties are: sampler geometry and material, in particular the shape of the rim; sink properties for gases and aerosols; and microbial transformations of the collected samples. An adequate number of replicates allows the identification of samples which are contaminated, in particular by bird droppings. The paper discusses physical and chemical properties of the samplers themselves. The dependence of measurement accuracy on the number of replicates and the sampling area exposed is discussed. Recommendations are given for sampling strategies, and for making corrections and substitution of missing data.     

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.     

Monitoring and modelling of biosphere/atmosphere exchange of gases and aerosols in Europe

Monitoring and modelling of deposition of air pollutants is essential to develop and evaluate policies to abate the effects related to air pollution and to determine the losses of pollutants from the atmosphere. Techniques for monitoring wet deposition fluxes are widely applied. A recent intercomparison experiment, however, showed that the uncertainty in wet deposition is relatively high, up to 40%, apart from the fact that most samplers are biased because of a dry deposition contribution. Wet deposition amounts to about 80% of the total deposition in Europe with a range of 10-90% and uncertainty should therefore be decreased. During recent years the monitoring of dry deposition has become possible. Three sites have been operational for 5 years. The data are useful for model development, but also for model evaluation and monitoring of progress in policy. Data show a decline in SO(2) dry deposition, whereas nitrogen deposition remained constant. Furthermore, surface affinities for pollutants changed leading to changes in deposition. Deposition models have been further developed and tested with dry deposition measurements and total deposition measurements on forests as derived from throughfall data. The comparison is reasonable given the measurement uncertainties. Progress in ozone surface exchange modelling and monitoring shows that stomatal uptake can be quantified with reasonable accuracy, but external surface uptake yields highest uncertainty.     

Modelling the accumulation of hydrophobic organic chemicals in earthworms

In this paper a method is developed which can be used to estimate the body burden of organic hydrophobic chemicals in earthworms. In contrast to the equilibrium partitioning theory, two routes of uptake are incorporated: uptake from interstitial water and dietary uptake. Although many uncertainties still remain, calculations show that for earthworms steady state body burdens are mainly determined by uptake from interstitial water. Under most circumstances, the contribution of dietary uptake is small, except for hydrophobic chemicals (log K_ow > 5) in soils with a high organic matter (OM) content of ≈ 20 %. Under those conditions, estimates of the steady state body burden calculated with the equilibrium partitioning model, in which only uptake from interstitial water is taken into account, might result in a small underestimation of the real body burden of chemicals in earthworms.     

Hydrophobicity of complex organic mixtures

Hydrophobicity is an important property in risk assessment of chemicals. A group parameter that reflects the hydrophobicity of technical mixtures is not yet available. However, many substances are complex organic mixtures, for which it is practically impossible to determine each component separately. An experimental procedure to measure the hydrophobicity of organic mixtures without knowledge of the individual components was developed and tested for a mixture of benzene and twelve chlorobenzenes. This procedure is based on separation of the mixture into fractions of increasing hydrophobicity by reversed-phase HPLC, after which the total molar concentration in each fraction is determined by vapour pressure osmometry. The obtained information on hydrophobicity can be used for assessing bioaccumulation and sediment sorption after emission of the mixture to water has occurred.     

Uptake and elimination kinetics of triphenyltin hydroxide by two fish species

The uptake from water and the elimination of carbon‐14 radiolabelled triphenyltin hydroxide ([¹⁴C]TPTH) was studied in two fish species: guppy (Poecilia reticulata) and rainbow trout larvae (Salmo gairdneri). During all the experiments no steady state in fish was found. TPTH was rapidly taken up, while elimination was very slow. Uptake and elimination rate constants (k ₁ and k ₂, respectively), and a bioconcentration factor were estimated, assuming first order kinetics.

During eight days of exposure of guppy to TPTH an uptake rate constant k ₁ of 70±7L/kg.d and an elimination rate constant k ₂ of 0.005 ±0.029d ^‐1 was found. This resulted in a biconcentration factor of at least 2.1 × 10³L/kg (wet weight). Comparable results were obtained during a 30 days exposure experiment with guppy: k ₁ was 41±2L/kg.d, k ₂ 0.014 + 0.002d^‐1, and the bioconcentration factor was estimated to be 2.9 × 10³ L/kg (wet weight).

Four days exposure of rainbow trout larvae resulted in a it, of 22+ 2 L/kg.d, and a k ₂ of 0.031 ±0.007d^‐1. Using these k, and k ₂ values it was estimated that the biconcentration factor exceeds 650 L/kg (wet weight).