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.     

Treatment of chlorinated solvents by TiO2 photocatalysis and photo-Fenton: influence of operating conditions in a solar pilot plant

Titanium dioxide photocatalysis (using 20 0mg l(-1) of TiO2), under aerobic and anaerobic conditions, and photo-Fenton (2 and 56 mg l(-1) iron) were applied to the treatment of different NBCS (non-biodegradable chlorinated solvents), such as dichloroethane, dichloromethane and trichloromethane dissolved in water at 50 mg l(-1). All the tests were performed in a 35-l solar pilot plant with compound parabolic collectors (CPCs) under natural illumination. The two solar treatments were compared with attention to chloride release and TOC mineralisation, as the main parameters. Photo-Fenton was found to be the more appropriate treatment for these compounds, assuming volatilisation as a drawback of photocatalytic degradation of NBCS dissolved in water. In this context, several operating parameters related to NBCS degradation, e.g., treatment time, temperature, hydrogen peroxide consumption and volatility of parent compounds are discussed. The correct choice of operating conditions can very often diminish the problem of volatilisation during treatment.     

Distribution of organotin compounds in tissues of mussels Mytilus edulis and clams Mya arenaria

Concentrations and composition of butyltin (BT) and phenyltin (PT) compounds were compared in tissues of mussels Mytilus edulis and clams Mya arenaria collected from the Mersey Estuary. Tributyltin (TBT) concentrations were consistently highest in digestive gland and low in muscular tissues such as siphons (Mya) and adductor muscle (Mytilus). Lowest concentrations were found in the periostracum surrounding the siphons of Mya. Ratios of monobutyltin (MBT), dibutyltin (DBT) and TBT to total BT content of Mytilus tissues were in the ranges 25-34%, 21-28% and 44-51%, respectively. Much higher proportions of TBT:total BT were characteristic of Mya (>80% in the digestive gland, remaining tissue and gonad) implying that slow degradation rates account for the relatively high levels of TBT in this species. TPT was the only phenyltin compound detected (albeit at relatively low levels), and, like TBT, was present in highest concentrations in the digestive gland of clams--suggesting an important dietary component in the accumulation of OTs in these bivalves.     

Catalytic and electrocatalytic hydrogenolysis of brominated diphenyl ethers

Polybrominated diphenyl ethers (PBDEs) are ubiquitous environmental contaminants due to their use as additive flame-retardants. Conventional catalytic hydrogenolysis in methanol solution and electrocatalytic hydrogenolysis in aqueous methanol were examined as methods for debrominating mono- and di-bromodiphenyl ethers, as well as a commercial penta-PBDE mixture, in each case using palladium on alumina as the catalyst. Electrocatalytic hydrogenolysis employed a divided flow-through batch cell, with reticulated vitreous carbon cathodes and IrO2/Ti dimensionally stable anodes. Both methods gave efficient sequential debromination, with essentially complete removal of bromine from the PBDEs, but the electrocatalytic method was limited by the poor solubility of PBDEs in aqueous methanol.     

Using thermal units for estimating critical period of weed competition in off-season maize crop

Brazilian off-season maize production is characterized by low yield due to several factors, such as climate variability and inadequate management practices, specifically weed management. Thus, the goal of this study was to determinate the critical period of weed competition in off-season maize (Zea mays L.) crop using thermal units or growing degree days (GDD) approach to characterize crop growth and development. The study was carried out in experimental area of the University of S?o Paulo, Brazil, with weed control (C), as well as seven coexistence periods, 2, 4, 6, 8, and 12 leaves, flowering, and all crop cycle; fourteen treatments were done. Climate data were obtained from a weather station located close to the experimental area. To determine the critical period for weed control (CPWC) logistic models were fitted to yield data obtained in both W and C, as a function of GDD. For an arbitrary maximum yield loss fixed in 2.5%, the CPWC was found between 301 and 484 GDD (7-8 leaves). Also, when the arbitrary loss yield was fixed in 5 and 10%, the period before interference (PBI) was higher than the critical weed-free period (CWFP), suggesting that the weeds control can be done with only one application, between 144 and 410 GDD and 131 and 444 GDD (3-8 leaves), respectively. The GDD approach to characterize crop growth and development was successfully used to determine the critical period of weeds control in maize sown off-season. Further works will be necessary to better characterize the interaction and complexity of maize sown off-season with weeds. However, these results are encouraging because the possibility of the results to be extrapolated and because the potential of the method on providing important results to researchers, specifically crop modelers.     

The effect of EDTA on Helianthus annuus uptake, selectivity, and translocation of heavy metals when grown in Ohio, New Mexico and Colombia soils

The use of two EDTA concentrations for enhancing the bioavailability of cadmium, chromium, and nickel in three natural soils (Ohio, New Mexico and Colombia) was investigated. The resulting uptake, translocation and selectivity with Helianthus annuus after mobilization were also examined. In general, plants grown in the sandy-loam Ohio soil had a higher uptake that resulted in a selectivity and total metal content of Cd>Cr>Ni and 0.73 mg and Cr>Cd>Ni and 0.32 mg for 0.1 and 0.3 g kg-1 EDTA, respectively. With the silty-loam New Mexico soil, although the total metal uptake was not statistically different the EDTA level did alter the selectivity; Cd>Cr>Ni (0.1 g kg-1 EDTA) and Cd>Cr>Ni (0.3 g kg-1 EDTA). Conversely, with the Colombian (sandy clay loam) soil increasing the EDTA level resulted in a higher total metal uptake (0.62 mg) than the 0.1 g kg-1 (0.59 mg) treatment. For all three soils, the translocation of Cd was limited. Evaluating the mobile metal fraction with and without EDTA determined that the chelator was capable of overcoming mass transfer limitations associated with the expandable clay fraction in the soils. Root wash results and root biomass concentrations indicated that Cd sorption was occurring. Therefore limited Cd translocation was attributed to insufficient phytochelatin levels.     

Accumulation of trinitrotoluene (TNT) in aquatic organisms: part 2--Bioconcentration in aquatic invertebrates and potential for trophic transfer to channel catfish (Ictalurus punctatus)

The potential of TNT to accumulate in aquatic organisms was assessed by determining bioconcentration factors for TNT and TNT biotransformation products using two benthic invertebrates (Chironomus tentans and Lumbriculus variegatus), and by determining the bioaccumulation factor of TNT and TNT biotransformation products due to TNT exposure via feeding for channel catfish (Ictalurus punctatus). In all three species, TNT was rapidly biotransformed resulting in minimal accumulation. The bioconcentration factors for parent TNT ranged from 3 to 4 ml g(-1) for the invertebrates studied, while the TNT bioaccumulation factor for catfish via oral exposure of food pellets was 2.4x10(-5) g g(-1) based on the concentration of TNT in the food pellet. As indicated by this small bioaccumulation factor, TNT accumulation in channel catfish through trophic transfer would be negligible compared to aqueous exposure (previously reported BCF of 0.79 ml g(-1)). TNT extractable biotransformation products accumulated to a greater degree than parent TNT for all three species. In addition, a large fraction of the radioactivity within all three species resisted solvent extraction. The highest bioconcentration factors occurred in L. variegatus with extractable radioactivity measuring 76 ml g(-1) and total radioactivity measuring 216 ml g(-1). Because the bioaccumulation of TNT is very low compared to the bioaccumulation of its biotransformation products, further research including identifying and determining the relative toxicities of these biotransformation products is necessary to fully evaluate the environmental risk posed by exposure to TNT.     

Physical versus chemical effects on bacterial and bromide transport as determined from on site sediment column pulse experiments

Twenty-eight bacterial and Br transport experiments were performed in the field to determine the effects of physical and chemical heterogeneity of the aquifer sediment. The experiments were performed using groundwater from two field locations to examine the effects of groundwater chemistry on transport. Groundwater was extracted from multilevel samplers and pumped through 7-cm-long columns of intact sediment or repacked sieved and coated or uncoated sediment from the underlying aquifer. Two bacterial strains, Comamonas sp. DA001 and Paenibacillus polymyxa FER-02, were injected along with Br into the influent end of columns to examine the effect of cell morphology and cell surface properties on bacterial transport. The effects of column sediment grain size and mineral coatings coupled with groundwater geochemistry were also investigated. Significant irreversible attachment of DA001 was observed in the Fe oxyhydroxide-coated columns, but only in the suboxic groundwater where the concentrations of dissolved organic carbon (DOC) were ca. 1 ppm. In the oxic groundwater where DOC was ca. 8 ppm, little attachment of DA001 to the Fe oxyhydroxide-coated columns was observed. This indicates that DOC can significantly reduce bacterial attachment due electrostatic interactions. The larger and more negatively charged FER-02 displayed increasing attachment with decreasing grain size regardless of DOC concentration, and modeling of FER-02 attachment revealed that the presence of Fe and Al coatings on the sediment also promoted attachment. Finally, the presence of Al coatings and Al containing minerals appeared to significantly retard the Br tracer regardless of the concentration of DOC. These findings suggest that DOC in shallow oxic groundwater aquifers can significantly enhance the transport of bacteria by reducing attachment to Fe, Mn and Al oxyhydroxides. This effect appears to be profound for weakly and strongly charged hydrophilic bacteria and may contribute to differences in observations between laboratory experiments versus field-scale investigations particularly if the groundwater pH remains subneutral and Fe oxyhydroxide phases exist. These observation validate the novel approach taken in the experiments outlined here of performing laboratory-scale experiments on site to facilitate the use of fresh groundwater and thus be more representative of in situ groundwater conditions.     

Reduction of silver solubility by humic acid and thiol ligands during acanthite (beta-Ag2S) dissolution

Precipitation of highly insoluble metal sulfide minerals like acanthite (beta-Ag2S) or red cinnabar (HgS) is in principle an effective means to reduce metal availability and toxicity in contaminated soils. Unfortunately, experiments have shown that red cinnabar may be solubilized in the presence of dissolved organic matter or thiol ligands. To determine whether the same applies to acanthite, a laboratory synthesized beta-Ag2S mineral was incubated for up to 3 weeks in the presence of KNO3, dissolved humic acids, cysteine, methionine and thiosulfate. XPS analysis identified Ag2O (52%), Ag2SO4 (8%) and Ag2S (40%) on the particle surfaces. Ag was released into solution in the presence of KNO3 and methionine, presumably from mixed-oxidation surface layers. Contrary to earlier results with cinnabar, however, humic acids reduced Ag concentrations in solution by about 75%, and cysteine and thiosulfate, each containing a free -SH functional group, almost completely suppressed Ag release into solution.     

Are N and S deposition altering the mineral composition of Norway spruce and Scots pine needles in Finland?

Data from a large-scale foliar survey were used to calculate the extent to which N and S deposition determined the mineral composition of Scots pine and Norway spruce needles in Finland. Foliar data were available from 367 needle samples collected on 36 plots sampled almost annually between 1987 and 2000. A literature study of controlled experiments revealed that acidifying deposition mediates increasing N and S concentrations, and decreasing Mg:N and Ca:Al ratios in the needles. When this fingerprint for N and S elevated deposition on tree foliage was observed simultaneously with increased N and S inputs, it was considered sufficient evidence for assuming that acidifying deposition had altered the mineral composition of tree needles on that plot in the given year. Evidence for deposition-induced changes in the mineral composition of tree foliage was calculated on the basis of a simple frequency model. In the late eighties the evidence was found on 43% of the Norway spruce and 27% of Scots pine plots. The proportion of changed needle mineral composition decreased to below 8% for both species in the late nineties.