Solubility of lead, zinc and copper added to mineral soils

Elevated levels of heavy metals in soils are a result of industrial activities, atmospheric deposition, and the land application of sewage sludges and industrial by-products. Their persistence in the soil environment has created interest in the possible changes in solubility. In this study, total dissolved concentrations of Pb, Zn, and Cu were monitored in seven metal-amended soils (a calcareous and six acid mineral soils). Single metal solutions were added to soils and equilibrated (aged) for 40 days. During the 40 days the soil was allowed to air-dry and was rewetted in cycles of about 5 days. At the end of this reaction period, metal solubility was measured (by atomic absorption spectrometry and direct current plasma spectrometry) at the initial soil pH and at decreased pH values which were induced by addition of small aliquots of acid. As expected, solubility of added Pb, Zn, and Cu increased with a decrease in pH. Furthermore, the results showed that the solubility relationship with pH was similar in all non-calcareous soils. This suggests that metal solubility may be controlled by similar soil components, presumably involving soil characteristics such as pH, organic matter content, and soil mineralogy. For each metal, an approximate pH value was found at which solubility deviated from the solubility of metals when they occur in soils at typical (natural) values. This pH was about (pH+/-0.2): 5.2 for Pb, 6.2 for Zn, and 5.5 for Cu. Thus, pH values below these thresholds may enhance metal mobility, biological availability and toxicity in soils. Metals dissolved at higher pH in the calcareous soil (18.8 g kg(-1) inorganic carbon, initial pH 8.2). In a calcareous soil, a significant fraction of these metals react with carbonates, and decreased pH results in much higher metal dissolution. Yet, metal solubility in soils is not determined by the formation and dissolution of single metal compounds.     

Separation of non-ortho polychlorinated biphenyl congeners on pre-packed carbon tubes. Application to analysis in sewage sludge and soil samples

The analysis of planar (non-ortho) polychlorinated biphenyls (PCB) by HRGC-ECD or HRGC-HRMS requires a fractionation step to avoid the interferences of the bulk of PCB, usually in much higher concentration than the planar ones. In this paper, a new method, based on the fractionation of PCB on SPE commercial tubes pre-packed with Carbopack B, has been developed. After the extract has been applied on the stationary phase, the bulk of PCD are eluted with 15 ml of hexane (fraction I), mono-ortho PCB with 20 ml of hexane/toluene 99:1 (fraction II) and planar PCB with 20 ml of toluene (fraction III) in a station under vacuum. The method has been validated: accuracy (expressed as recovery in %) is >70% and precision (expressed as % RSD) is <20% considering changes of day, analyst and batch of tubes. The method is linear in the range studied. Other advantages are that the method is simple, rapid and it can be easily automated. The application of this separation to the determination of planar PCB in fly-ash extracts from an intercalibration exercise and to sewage sludge, sediment and soil samples has been successful. In addition, this method removes hydrocarbons from the planar PCB fraction and allows its concentration to very small volumes.     

Probabilistic human health risk of PCDD/F exposure: a socioeconomic assessment

The aim of the present study was to assess the human health risks (carcinogenic and non-carcinogenic) of PCDD/F exposure for the adult population living in two different areas (industrial and residential) of Tarragona (Catalonia, Spain), as well as to compare these risks according to the socioeconomic status of the population. Two pathways were considered for PCDD/F exposure: direct (air inhalation, dermal contact and ingestion from soils and dust) and dietary. Although environmental exposure was higher for the population living in the neighborhood of the industrial area (mainly lower socioeconomic group subjects), it only accounted 1.05%. On the other hand, PCDD/F exposure through dietary intake was more important for those individuals of an upper socioeconomic level. This was due to the fact that their diet is richer in those foodstuffs containing higher PCDD/F concentrations. Consequently, taking together direct and dietary exposure to PCDD/Fs, the result is that upper socioeconomic group populations are more exposed to these toxic pollutants. In any case, the current levels of PCDD/F exposure would not mean significant carcinogenic and non-carcinogenic risks for the population living in the industrial and residential areas of Tarragona.     

Patterns and levels of halogenated volatile compounds in Portuguese surface waters

The present study focused on monitoring the concentration of 14 halogenated volatile organic compounds in surface waters, including sea, estuarine, river water and industrial effluents in order to determine the most ubiquitous compounds and their concentration levels, which were used to establish their geographical and temporal distribution. EPA Method 502, based on purge and trap techniques, was used. In this method volatile organic pollutants are extracted (purged) from the water sample by bubbling inert gas through the aqueous sample. Purged sample components are trapped in a cartridge containing the polymeric sorbent Tenax and, thereafter, the cartridge is heated and backflushed with helium to desorb the trapped sample components directly into a gas chromatograph with electron capture detector (GC-ECD). The linearity range of the method varied from 0.1 to 4 microg L(-1) with a limit of detection at the low microg L(-1) level. The present study consisted of a monthly monitoring of 46 points throughout Portugal, during 14 months. Chloroform was found in 50% of the samples analyzed, its presence being correlated to both agricultural and industrial activities. Other compounds detected were tetrachloroethylene, trichloroethylene, carbon tetrachloride and 1,2,4 trichlorobenzene, which were present in 10-20% of the samples at concentrations up to 18 microg L(-1). 1,1,2,2-Tetrachloroethane and its degradation product 1,1,2-trichloroethane were found in 5% of the samples, the levels of the latter being higher than those of the parent compound in most samples. Sporadic high concentrations of some volatile halogenated organic compounds were attributed to local uses as solvents.     

Chemical availability of mercury in stream sediments from the Almadén area, Spain

The chemical speciation, fractionation and availability of mercury in sediments from a cinnabar mining area (Almadén, Spain) was studied with different extraction and analytical procedures, in order to determine the degree to which the ecosystem is harmed by this pollutant. Three total extraction procedures, a sequential extraction and the speciation of organo-mercury compounds were performed in nine sediment samples. In the study area, although concentrations of mercury can be extremely high (up to 1,000 mg kg(-1)), no organomercury compounds were detected (< 2 microg kg(-1) and the availability of this element seems restricted. One of the methods for total extraction presented considerably lower recovery in Almadén's sediments, yet the results were controlled with certified reference materials. This disagreement was attributed to the fact that the mercury is in a refractory form. Sequential extraction was able to show that most of the mercury is associated with sulfides (probably as metacinnabar) or in the residual refractory phase (probably as red cinnabar).     

Estimation of the global evolution of atmospheric pollution in Salamanca (Spain) during the 1993-2001 period according to one global index (ORAQI)

The aim of this study has been to use a global index to measure the air quality in the city, apart from individual assessment of the values of the concentrations of the different pollutants. We calculated the ORAQI with the data obtained at four air-pollution monitoring stations located in the city of Salamanca over the period between 1993 and 2001. For the calculations, SO2, PM10, NO2, CO and O3 were used as the most significant pollutants for the surroundings of the monitoring stations. The evolution of this index over 9 years is reported, and the repercussion of the most characteristic pollutants of each season of the year on the ORAQI along the whole period analysed is studied. The importance of the summer pollution in the characterisation of the least polluted surroundings was observed. At the most polluted sites, a decrease in the values corresponding to winter occurs, leading the ORAQI to take similar values along the whole year. In general, taking into account the surroundings of all the monitoring stations, the quality of the air to which the inhabitants of the city of Salamanca are exposed to can be said to be good.     

Di-(2-ethylhexyl)phthalate in sewage sludge and post-treated sludge: quantitative determination by HRGC-MS and mass spectral characterization

DEHP was quantified into sewage sludge, thermally dried sludge and compost samples from different areas of Catalonia (North East Spain) using high-resolution gas chromatography (HRGC) coupled to a mass spectrometry (MS). The aim of the work was to determine the evolution of this ubiquitous environmental contaminant along some post-treatment sludge processes, such as composting and thermally drying. DEHP concentration detected in some sludges are above the maximum limit suggested by the EC (100 ppm d.m.) for agricultural use. However, the composting and thermally drying reduce the amount of DEHP in sewage sludge to acceptable level for safe land application. The study was completed with the characterization and long-term observation of DEHP in sewage sludge, composted sludge and thermally dried sludge mixed with two types of soils. In all cases, the percentage of DEHP degraded was higher than 50% after 9 months of incubation.     

Detoxification of semisolid olive-mill wastes and pine-chip mixtures using Phanerochaete flavido-alba

Semisolid olive-mill residues, pine chips, and mixtures of both residues contain phytotoxic components capable of inhibiting germination and vegetative growth in plants. Solid-state cultures of Phanerochate flavido-alba on pine chips or mixtures of both residues reduce these phytotoxic effects in fermented substrates. The phenol and lipid contents in cultures detoxified by this fungus also decreases.     

A kinetic study of anaerobic digestion of olive mill wastewater at mesophilic and thermophilic temperatures

The kinetics of the anaerobic digestion of olive mill wastewater (OMW) was studied in the mesophilic and thermophilic ranges of temperature. Two completely mixed continuous flow bioreactors operating at 35 degrees C and 55 degrees C and with an average biomass concentration of 5.45 g VSS litre(-1) were used. The thermophilic reactor worked satisfactorily between hydraulic retention times (HRT) of 10 to 40 days, removing between 94.6 and 84.4% of the initial chemical oxygen demand (COD). In contrast, the mesophilic reactor showed a marked decrease in substrate utilization and methane production at a HRT of 10 days. TVFA levels and the TVFA/alkalinity ratio were higher and close to the suggested limits for digester failure. The yield coefficient for methane production (1 CH(4) STP g(-1) COD(added)) was 28% higher in the thermophilic process than in the mesophilic one. Macroenergetic parameters, calculated using Guiot's kinetic model, gave yield coefficients for the biomass (Y) of 0.18 (mesophilic) and 0.06 g VSS g(-1) COD (thermophilic) and specific rates of substrate uptake for cell maintenance (m) of 0.12 (mesophilic) and 0.27 g COD g(-1) VSS.day(-1) (thermophilic). The experimental results showed the rate of substrate uptake (R(s); g COD g(-1) VSS.day(-1)), correlated with the concentration of biodegradable substrate (S(b); g COD litre(-1)), through an equation of the Michaelis-Menten type for the two temperatures used.     

The algal community as an indicator of the trophic status of Lake Patzcuaro, Mexico

An evaluation of water quality and phytoplankton composition position was carried out in order to determine the trophic conditions of Lake Patzcuaro (2035 m above sea level), a high altitude tropical lake. Temperatures ranged from 15 to 23 degrees C. Total phosphorus and inorganic nitrogen showed a seasonal variation; highest values coincided with the rainy season (0.48 and 2.1 mg litre(-1), respectively). Dissolved oxygen ranged from 2 to 7.9 mg litre(-1) at the surface and from 0.6 to 7.3 mg litre(-1) on the bottom, the lowest values being found in shallow zones. Average transparency varied from 0.62 to 1.4 m Secchi depth. Rainfall was a primary factor in seasonal variability as it influenced both physical and biological conditions by contributing to the transport and deposition of silt, which mixed with sinking algal cells. The composition of the surface phytoplankton segregated along five major divisions comprising a total of 49 species. General seasonal patterns of dominance alternated in a sequence beginning with Bacillariophyta, through Chlorophyta to Cyanophyta. Diatoms, the dominant group from February to early June, included Melosira granulata, Stephanodiscus sp., Synedra sp. and Fragilaria sp. During the rainy season (late June to September), Microcystis aeruginosa, Oscillatoria sp., Anabaena sp., Merismopedia sp., Crucigenia cuadrata, Oocystis lacustris, Selenastrum gracile, Mallomonas sp. and Tetraediella sp. were important. Melosira granulata was present throughout the period of study. Spatial and temporal variability in both physical and biological conditions make it difficult to assign a specific trophic state to Lake Patzcuaro. Nevertheless, analysis of the algal community indicates a generally mesotrophic condition.