Dissolved organic matter fractions formed during composting of winery and distillery residues: evaluation of the process by fluorescence excitation-emission matrix

The aim of the present paper is to assess the maturity degree reached by different samples of several mixtures from winery and distillery residues composted using the Rutgers composting system, by means of excitation-emission matrix (EEM) fluorescence spectroscopy. The composts were sampled once a week for about 200d. EEM spectra indicate the presence of different fluorophores. The fluorescence intensities of these peaks show trends related to the maturity of the composting samples selected. The "contour density" of EEM maps is strongly modified through time. We have used the quantitative method of fluorescence regional integration (FRI). The EEMs were delineated into five excitation-emission regions. The degree of compost maturity could be correlated with the percentage of the volumetric integration under the EEM within each region. Further refinement of these techniques should provide a relatively rapid method for assessing the suitability of the compost to soil application.     

Quantifying road dust resuspension in urban environment by Multilinear Engine: A comparison with PMF2

Atmospheric PM pollution from traffic comprises not only direct emissions but also non-exhaust emissions because resuspension of road dust that can produce high human exposure to heavy metals, metalloids, and mineral matter. A key task for establishing mitigation or preventive measures is estimating the contribution of road dust resuspension to the atmospheric PM mixture. Several source apportionment studies, applying receptor modeling at urban background sites, have shown the difficulty in identifying a road dust source separately from other mineral sources or vehicular exhausts. The Multilinear Engine (ME-2) is a computer program that can solve the Positive Matrix Factorization (PMF) problem. ME-2 uses a programming language permitting the solution to be guided toward some possible targets that can be derived from a priori knowledge of sources (chemical profile, ratios, etc.). This feature makes it especially suitable for source apportionment studies where partial knowledge of the sources is available.In the present study ME-2 was applied to data from an urban background site of Barcelona (Spain) to quantify the contribution of road dust resuspension to PM₁₀ and PM_2.5 concentrations. Given that recently the emission profile of local resuspended road dust was obtained (Amato, F., Pandolfi, M., Viana, M., Querol, X., Alastuey, A., Moreno, T., 2009. Spatial and chemical patterns of PM₁₀ in road dust deposited in urban environment. Atmospheric Environment 43 (9), 1650–1659), such a priori information was introduced in the model as auxiliary terms of the object function to be minimized by the implementation of the so-called “pulling equations”.ME-2 permitted to enhance the basic PMF solution (obtained by PMF2) identifying, beside the seven sources of PMF2, the road dust source which accounted for 6.9 μg m^?3 (17%) in PM₁₀, 2.2 μg m^?3 (8%) of PM_2.5 and 0.3 μg m^?3 (2%) of PM₁. This reveals that resuspension was responsible of the 37%, 15% and 3% of total traffic emissions respectively in PM₁₀, PM_2.5 and PM₁. Therefore the overall traffic contribution resulted in 18 μg m^?3 (46%) in PM₁₀, 14 μg m^?3 (51%) in PM_2.5 and 8 μg m^?3 (48%) in PM₁. In PMF2 this mass explained by road dust resuspension was redistributed among the rest of sources, increasing mostly the mineral, secondary nitrate and aged sea salt contributions.     

The relationships between mercury and selenium in plankton and fish from a tropical food web

Background, aim, and scope  Selenium (Se) has been shown to reduce mercury (Hg) bioavailability and trophic transfer in aquatic ecosystems. The study of methylmercury (MeHg) and Se bioaccumulation by plankton is therefore of great significance in order to obtain a better understanding of the estuarine processes concerning Hg and Se accumulation and biomagnification throughout the food web. In the western South Atlantic, few studies have documented trace element and MeHg in fish tissues. No previous study about trace elements and MeHg in plankton has been conducted concerning tropical marine food webs. Se, Hg, and MeHg were determined in two size classes of plankton, microplankton (70–290 μm) and mesoplankton (≥290 μm), and also in muscle tissues and livers of four fish species of different trophic levels (Mugil liza, a planktivorous fish; Bagre spp., an omnivorous fish; Micropogonias furnieri, a benthic carnivorous fish; and Centropomus undecimalis, a pelagic carnivorous fish) from a polluted estuary in the Brazilian Southeast coast, Guanabara Bay. Biological and ecological factors such as body length, feeding habits, and trophic transfer were considered in order to outline the relationships between these two elements. The differences in trace element levels among the different trophic levels were investigated. Materials and methods  Fish were collected from July 2004 to August 2005 at Guanabara Bay. Plankton was collected from six locations within the bay in August 2005. Total mercury (THg) was determined by cold vapor atomic absorption spectrometry (CV-AAS) with sodium borohydride as a reducing agent. MeHg analysis was conducted by digesting samples with an alcoholic potassium hydroxide solution followed by dithizone-toluene extraction. MeHg was then identified and quantified in the toluene layer by gas chromatography with an electron capture detector (GC-ECD). Se was determined by AAS using graphite tube with Pin platform and Zeeman background correction. Results and discussion  Total mercury, MeHg, and Se increased with plankton size class. THg and Se values were below 2.0 and 4.8 μg g⁻¹ dry wt in microplankton and mesoplankton, respectively. A large excess of molar concentrations of Se in relation to THg was observed in both plankton size class and both fish tissues. Plankton presented the lowest concentrations of this element. In fish, the liver showed the highest THg and Se concentrations. THg and Se in muscle were higher in Centropomus undecimalis (3.4 and 25.5 nmol g⁻¹) than in Micropogonias furnieri (2.9 and 15.3 nmol g⁻¹), Bagre spp (1.3 and 3.4 nmol g⁻¹) and Mugil liza (0.3 and 5.1 nmol g⁻¹), respectively. The trophic transfer of THg and Se was observed between trophic levels from prey (considering microplankton and mesoplankton) to top predator (fish). The top predators in this ecosystem, Centropomus undecimalis and Micropogonias furnieri, presented similar MeHg concentrations in muscles and liver. Microplankton presented lower ratios of methylmercury to total mercury concentration (MeHg/THg) (34%) than those found in mesoplankton (69%) and in the muscle of planktivorous fish, Mugil liza (56%). The other fish species presented similar MeHg/THg in muscle tissue (of around 100%). M. liza showed lower MeHg/THg in the liver than C. undecimalis (35%), M. furnieri (31%) and Bagre spp. (22%). Significant positive linear relationships were observed between the molar concentrations of THg and Se in the muscle tissue of M. furnieri and M. liza. These fish species also showed significant inverse linear relationships between hepatic MeHg and Se, suggesting a strong antagonistic effect of Se on MeHg assimilation and accumulation. Conclusions  Differences found among the concentrations THg, MeHg, and Se in microplankton, mesozooplankton, and fishes were probably related to the preferred prey and bioavailability of these elements in the marine environment. The increasing concentration of MeHg and Se at successively higher trophic levels of the food web of Guanabara Bay corresponds to a transfer between trophic levels from the lower trophic level to the top-level predator, suggesting that MeHg and Se were biomagnified throughout the food web. Hg and Se were positively correlated with the fish standard length, suggesting that larger and older fish bioaccumulated more of these trace elements. THg, MeHg, and Se were a function of the plankton size. Recommendations and perspectives  There is a need to assess the role of selenium in mercury accumulation in tropical ecosystems. Without further studies of the speciation of selenium in livers of fishes from this region, the precise role of this element, if any, cannot be verified in positively affecting mercury accumulation. Further studies of this element in the study of marine species should include liver samples containing relatively high concentrations of mercury. A basin-wide survey of selenium in fishes is also recommended.     

In situ assays with tropical cladocerans to evaluate edge-of-field pesticide runoff toxicity

Tropical regions’ economy is usually based on agriculture, which involves an intensive use, and even frequent overuse, of pesticides. Nevertheless, not much research has been done on the impact of pesticides on tropical aquatic ecosystems, which are often contaminated by runoff-related pesticide inputs due to unpredictable and torrential rainfalls. This study aimed to: (i) adapt and evaluate a short-term sublethal in situ assay using post-exposure feeding as an endpoint, to the tropical cladoceran species Diaphanosoma brachyurum (collected at the Pedra do Cavalo dam in the Paraguaçu River basin, Bahia, Brazil), and, (ii) assess the role of the standard species Daphnia magna as an adequate laboratory surrogate. Lethal and sublethal (post-exposure feeding) responses were assessed for the two species. To evaluate these responses under environmentally realistic exposure conditions, a runoff event was simulated in an agricultural area previously contaminated with different deltamethrin concentrations. The resultant runoff water was used to set up microcosms with different dilutions, simulating the entrance of runoff water in an adjacent lentic system. An in situ assay with D. brachyurum was performed inside the microcosms, allowing to discriminate the effects due to deltamethrin from those due to other potential stressors associated with the experimental design (e.g. organism handling, load of suspended particles, microcosm design). Water samples were collected from microcosms to conduct a laboratory assay with D. magna. The in situ methodologies revealed to be suitable to conduct assays with D. brachyurum under tropical conditions, since all exposed organisms were successfully retrieved from the chambers. Furthermore, none of the potential stressors associated with the experimental design influenced the daphnids’ performance. The tropical cladoceran species, exposed under more realistic conditions, revealed to be more sensitive than the laboratory standard species: lethal effects were only observed for D. brachyurum and sublethal effects were noticed at a lower deltamethrin concentration for this species than for D. magna.     

Nutrient accumulation in trees and soil following irrigation with municipal effluent in Australia

Irrigation of tree crops is being evaluated as a method of land disposal of municipal effluent in Australia. A study was carried out from 1980-84 in which seven tree species were sprinkler-irrigated with effluent at an annual rate of 1191-1752 mm. Effective weed control and frequent irrigation resulted in good survival of all species (range 83-100%) at 12 months. Total productivity was estimated at age 4 years by measuring biomass of each species inclusive of litter and roots to a soil depth of 80 cm. Biomass production of the high-yielding species, flooded gum (Eucalyptus grandis) and Sydney blue gum (E. saligna), was around 10 kg m(-2). Percentage leaf mass of these species was small (8-9%) compared with 25% and 29% for the relatively slow-growing river she-oak (Casuarina cunninghamiana) and radiata pine (Pinus radiata). Accumulation of nutrients in the total biomass differed significantly between species and ranged from 34-54 g m(-2) for nitrogen, 4.0-10.4 g m(-2) for phosphorus, 2.1-12.2 g m(-2) for sodium, 22-34 g m(-2) for potassium, 12-61 g m(-2) for calcium and 4.7-9.3 g m(-2) for magnesium. River she-oak and river red gum (E. camaldulensis), because of their relatively large crown and litter masses, accumulated more nitrogen, phosphorus, potassium and calcium than flooded gum or Sydney blue gum. Chemical properties of soils (0-150 cm) were measured in 1980 and again in 1984. Irrigation significantly increased pH (by around 1 unit), throughout the profile. Concentrations of total phosphorus, and exchangeable sodium, calcium and magnesium were increased in the upper profile. Overall, soil chemical properties were not adversely affected by effluent irrigation over the 4-year period, though there was a trend towards more sodic conditions in the soil profile. Nutrient accumulation in soil occurred mainly in the 0-35 cm depth, coinciding with the main root zone of the trees. Renovation of the effluent was therefore estimated as the amount of each nutrient accumulated in the biomass (averaged over the seven species) plus soil (0-35 cm), expressed as a percentage of amount applied in irrigation over the 4 years; that is, nitrogen, 29%; phosphorus, 78%; sodium, 15%; potassium, 26%; calcium, 98% and magnesium, 54%.     

The sensitivity of surface waters of Great Britain to acidification predicted from catchment characteristics

Using a combination of soil, land use and geological information, a map of Great Britain has been derived which indicates the sensitivity of surface waters to acidification. For the geological information, a slightly modified version of an available map was used which indicated the sensitivity of groundwaters to acidification. For soils, 1-km databases of soil information for England and Wales and for Scotland were employed to map the soil sensitivity as determined by buffering capacity. The derived soils map was modified to take account of agricultural liming in arable and managed grassland areas using the ITE Land Classification. The final map of surface water sensitivity was obtained by using a geographic information system overlay procedure which enabled each combination of soil and geology sensitivity to be uniquely defined. The final sensitivity classification was based upon expert knowledge and the experience of a similar sensitivity mapping exercise for Wales.     

Occurrence and treatment trials of endocrine disrupting chemicals (EDCs) in wastewaters

This study demonstrates that both synthetic and natural endocrine disrupting chemicals (EDCs) (e.g., bisphenol A, estrone and 17beta-estradiol) were found in the crude wastewaters from two wastewater treatment works (WwTWs). Conventional biological processes can lower EDCs concentrations to several tens to hundreds ngl(-1). Since natural EDCs (e.g., estrone and 17beta-estradiol) have biological activity and adverse impact on the environment at extremely low concentrations (several tens of ngl(-1)), further treatment after conventional biological processes is required. Preliminary trials with ferrate(VI) and electrochemical oxidation process demonstrated that both processes can effectively reduce EDCs to very low levels, ranging between 10 and 100ngl(-1), but the former is more effective than the latter to reduce COD concentration in wastewater for given studying conditions.     

Bacteria transport and deposition under unsaturated conditions: the role of the matrix grain size and the bacteria surface protein

Unsaturated (80% water saturated) packed column experiments were conducted to investigate the influence of grain size distribution and bacteria surface macromolecules on bacteria (Rhodococcus rhodochrous) transport and deposition mechanisms. Three sizes of silica sands were used in these transport experiments, and their median grain sizes were 607, 567, and 330 microm. The amount of retained bacteria increased with decreasing sand size, and most of the deposited bacteria were found adjacent to the column inlet. The deposition profiles were not consistent with predictions based on classical filtration theory. The experimental data could be accurately characterized using a mathematical model that accounted for first-order attachment, detachment, and time and depth-dependent straining processes. Visual observations of the bacteria deposition as well as mathematical modelling indicated that straining was the dominant mechanism of deposition in these sands (78-99.6% of the deposited bacteria), which may have been enhanced due to the tendency of this bacterium to form aggregates. An additional unsaturated experiment was conducted to better deduce the role of bacteria surface macromolecules on attachment and straining processes. In this case, the bacteria surface was treated using a proteolitic enzyme. This technique was assessed by examining the Fourier-transform infrared spectrum and hydrophobicity of untreated and enzyme treated cells. Both of these analytical procedures demonstrated that this enzymatic treatment removed the surface proteins and/or associated macromolecules. Transport and modelling studies conducted with the enzyme treated bacteria, revealed a decrease in attachment, but that straining was not significantly affected by this treatment.     

The occurrence of xenoestrogens in the Elbe river and the North Sea

The xenoestrogens Bisphenol A (BPA), p-alkylphenols and p-alkylphenol ethoxylates were determined in water samples of the North Sea, the Elbe river, and its tributaries Schwarze Elster, Mulde, Saale and the Weisse Elster. The sampling sites of the Elbe river reached from Schmilka at the German-Czech border to Cuxhaven at the estuary. Samples of the North Sea were taken in the German Bight. Additionally, freshly deposed sediments of the River Elbe and its tributaries were analyzed. Partitioning coefficients of these compounds for the distribution between suspended particulate matter (SPM) and the aqueous phase were calculated for samples of the River Elbe at sampling site Geesthacht. The analytical procedure consisted of liquid-liquid extractions of the acidified water samples using dichloromethane. Sediments and SPM samples were extracted by Accelerated Solvent Extraction with n-hexane/acetone. Following a clean-up by HPLC, the analytes were derivatized with heptafluorobutyric acid anhydride and quantified using GC-MSD. The concentration ranges of the compounds analyzed in water samples of the Elbe river were as follows (in ng l(-1)): BPA 9-776, alkylphenols 10-221 and alkylphenol ethoxylates 18-302. In sediment samples the concentrations were (in microg kg(-1) dry mass): BPA 66-343, alkylphenols 17-1378 and alkylphenol ethoxylates 30-1797. In samples of the North Sea the concentrations were generally about 1 order of magnitude lower. As shown by the concentration profiles following the River Elbe into the North Sea, the Elbe river must be considered as a major pollution source for the North Sea concerning the compounds analyzed. The SPM/water-partitioning coefficients calculated (mean values) amounted to: BPA 4.50, alkylphenols 5.52-5.58 and alkylphenol ethoxylates 5.60-6.38. A comparison of the results with data from other surface waters showed that concentrations of these xenoestrogens in the River Elbe and its tributaries were relatively low. The evaluation of the data based on the lowest observable effect concentration (LOEC) for alkylphenols (endpoint: vitellogenin synthesis in male trout) indicated that the concentrations were well below the effectivity threshold.