Feasibility study prior to the certification of trace elements in urban and industrial wastewater reference materials

Reliable results for the determination of trace elements in urban and industrial wastewaters are of paramount importance for both checking the performance of sewage treatment and for detecting possible urban or industrial contamination sources. The quality control of measurements should in principle rely on external tools such as certified reference materials (CRM), which should represent, as closely as possible, the matrix of samples currently analysed, e.g., in the frame of environmental monitoring. To date, however, no CRM representatives of wastewater composition are available, which limits the possibility for control laboratories to check their QC externally. To fill this gap, the European Commission's Standards, Measurements and Testing Programme (formerly BCR) has started a European collaborative project of which the aim is to test the feasibility of preparation of wastewater reference materials and the analytical state-of-the-art to enable the certification of trace elements in such matrices. This paper presents the results of the first phase of this project, namely the feasibility study and the results of an interlaboratory trial.     

Landsat image and sample design for water reservoirs (Rapel dam Central Chile)

Spatial heterogeneity of the Rapel reservoir surface waters is analyzed through Landsat images. The image digital counts are used with the aim or developing an aprioristic quantitative sample design.Natural horizontal stratification of the Rapel Reservoir (Central Chile) is produced mainly by suspended solids. The spatial heterogeneity conditions of the reservoir for the Spring 86-Summer 87 period were determined by qualitative analysis and image processing of the MSS Landsat, bands 1 and 3. The space-time variations of the different observed strata obtained with multitemporal image analysis.A random stratified sample design (r.s.s.d) was developed, based on the digital counts statistical analysis. Strata population size as well as the average, variance and sampling size of the digital counts were obtained by the r.s.s.d method.Stratification determined by analysis of satellite images were later correlated with ground data. Though the stratification of the reservoir is constant over time, the shape and size of the strata varys.     

Environmental Assessment of the Impact of Ozone to the Neuston of the Sea-Surface Microlayer of the Gulf of Mexico

Substantial amounts of NOx (146 000 t/y) and total hydrocarbons (294 000 t/y) are released to the marine atmosphere by the large number of oil and gas operations over Federal waters of the Gulf of Mexico (GOM). Under appropriate meteorological conditions these emissions react to form ozone (0–54 g/m3 over-water) which can affect the marine environment. Using a dry deposition model, this work examines the amount of ozone derived from oil and gas offshore operations and deposited in the sea surface of the Gulf of Mexico, and assesses its impact on the neuston of the sea-surface microlayer. Surface integrated estimates of ozone deposited from oil and gas operations over the sea surface ranges from 400 kg to 1800 kg which results in sea surface concentrations of 15 g/m3. This estimate and the actual toxic ozone levels suggest no acute, toxic impacts to the neuston. However, indirect effects may occur through changes to the pelagic foodwebs and organic carbon pathways. Another potential pathway for ozone impacting the environment is through the production of bromate. Based on the concentrations and time scales (11–139 days) only sublethal effects appear to occur, but uncertainties associated with this assessment need to be further studied. From an ecological perspective, the environmental impacts and risks of NOx and VOC discharges from offshore platforms need to be assessed for neuston and other components of the marine ecosystem.     

Stability and storage problems in organotin speciation in environmental samples

The stability of both tributyltin (TBT) and triphenyltin (TPT) in water, sediment, oysters and cockles was studied over a period of 18 months using several storage conditions. Butyltins were stable in unacidified sea-water stored in polycarbonate bottles in the dark at 4 degrees C for 7 months, but half of the TBT concentration was lost after 540 d. A comparable preservation time was achieved for butyltins stored on C18 cartridges at room temperature. However, phenyltins extracted from sea-water were stable for only 60 d stored on cartridges and even more pronounced losses (about 90% after 540 d) occurred when they were stored in either polycarbonate or Pyrex glass bottles. Losses of organotins were observed in sediments after air drying and pasteurization treatments using a freeze-dried sediment as a comparator, whereas both butyltin and phenyltin species remained stable in sediments stored at -20 degrees C for the 18 months tested, irrespective of the treatment used for stabilization. Air drying followed by pasteurization was shown to be superior to other treatments for the stabilization of organotin compounds in sediments stored at higher temperatures, but 30% of TBT was lost after 540 d at 25 degrees C. Finally, butyltins were stable in both frozen cockles and oysters in the dark over a 7 month period and in freeze-dried samples stored at 4 degrees C for 5 months, but TBT losses of about 70% were observed after 540 d.     

Microbial community dynamics in a chemolithotrophic denitrification reactor inoculated with methanogenic granular sludge

Denitrification is applied in the tertiary treatment of wastewater to reduce nitrogen pollution. Fluorescence in situ hybridization (FISH), catalyzed reporter deposition (CARD)-FISH, cloning, and scanning electron microscopy (SEM) were applied to follow the evolution of the microbial composition and structure of granular sludge in chemolithotrophic denitrifying bioreactors fed with nitrate and thiosulfate. FISH oligonucleotide probes for the chemolitoautotrophic denitrifiers Thiobacillus denitrificans and Thiomicrospira denitrificans were designed and their utility tested. CARD-FISH and cloning data showed that bacterial diversity in the biofilms changed during the reactor operation. Chemoorganotrophic fermentative Gram-positive strains in the phyla, Actinobacteria and Firmicutes, were dominant in the methanogenic inoculum, both in terms of biodiversity and in number. Other significant phyla were Bacteroidetes and Chloroflexi. After 6 months of operation, Proteobacteria became dominant (83% of the clones). The diversity of Gram-positive bacteria was partially maintained although their abundance decreased notably. After 110 d of operation, the abundance of Tb. denitrificans cells increased considerably, from 1% to 35% of total DAPI-stained cells and from no isolated clones to 15% of the total clones. Tm. denitrificans only represented a minor fraction of the microorganisms in the sludge (1-4% of the DAPI-stained cells). These findings confirm that Tb. denitrificans was the dominant chemolitoautotrophic denitrifying microorganism in the bioreactors. The Archaeal diversity remained almost unchanged and it was represented mostly by Methanosaeta soehngenii. SEM results indicated a considerable loss in the integrity of the sludge granules during the operation, with risk of sludge buoyancy.     

Influence of resorcinol chemical oxidation on the removal of resulting organic carbon by activated carbon adsorption

Activated carbon adsorption and chemical oxidation followed by activated carbon adsorption of resorcinol in water has been studied. Three chemical oxidants have been used: hypochlorite, permanganate and Fenton's reagent. The influence of concentrations of resorcinol and activated carbon on adsorption removal rates has been investigated. Both isotherm and adsorption kinetics have been studied. Results are fit well by Freundlich isotherms and adsorption rates of resorcinol were found to follow a pseudo-second-order kinetic model. However, pyrogallol, an intermediate of resorcinol oxidation with permanganate and Fenton's reagent, showed an unfavourable isotherm type. At the conditions investigated, chemical oxidation allows slight reductions of TOC and intermediates formed were found to inhibit the adsorption rate of TOC in the case of permanganate and Fenton's reagent oxidation, likely due to formation of some polymer pyrogallol product. The adsorption process was found to be controlled by pore internal diffusion, which justifies the poor affinity of oxidation intermediates toward activated carbon since molecules of larger size should diffuse rapidly for the adsorption to be effective.     

Solar TiO2-assisted photocatalytic degradation of IGCC power station effluents using a Fresnel lens

The heterogeneous TiO2 assisted photocatalytic degradation of wastewater from a thermoelectric power station under concentrated solar light irradiation using a Fresnel lens has been studied. The efficiency of photocatalytic degradation was determined from the analysis of cyanide and formate removal. Firstly, the influence of the initial concentration of H2O2 and TiO2 on the degradation kinetics of cyanides and formates was studied based on a factorial experimental design. Experimental kinetic constants were fitted using neural networks. Results showed that the photocatalytic process was effective for cyanides destruction (mainly following a molecular mechanism), whereas most of formates (degraded mainly via a radical path) remained unaffected. Finally, to improve formates degradation, the effect of lowering pH on their degradation rate was evaluated after complete cyanide destruction. The photooxidation efficiency of formates reaches a maximum at pH around 5-6. Above pH 6, formate anion is subjected to electrostatic repulsion with the negative surface of TiO2. At pH<4.5, formate adsorption and photon absorption are reduced due to some catalyst agglomeration.     

Spatial configuration of land-use/land-cover in the Pujal-Coy project area, Huasteca Potosina region, Mexico

This article analyzes the relationship between the configuration and spatial reorganization of land-use and land-cover in the Pujal-Coy project area, Huasteca Potosina region, eastern San Luis Potosí, Mexico, as well as the relationship between these changes and the environmental conditions prevailing in the area. Land-use and land-cover changes were determined through the analysis and interpretation of satellite images from different dates. The changes identified in the different study periods were correlated with the prevailing physical factors. The results show that the spatial configuration of farming activities, initially induced by the implementation of a regional development project, is highly correlated to the presence of limiting factors such as soil type, slope, and climate. Particularly, the former represents the element that has led to the establishment of the current distribution pattern of farming activities.     

Sources, transport and reactivity of anionic and non-ionic surfactants in several aquatic ecosystems in SW Spain: a comparative study

Presence, distribution and transport mechanisms of the four major synthetic surfactants -linear alkylbenzene sulfonates (LAS), alkyl ethoxysulfates (AES), nonylphenol ethoxylates (NPEOs) and alcohol ethoxylates (AEOs)- have been simultaneously studied in different aquatic ecosystems. Urban wastewater discharges and industrial activities were identified as the main sources for these compounds and their metabolites. LAS, AES and carboxylic metabolites remained in the dissolved form (87–99%). However, NPEOs and AEOs were mostly associated with particulate matter (65–86%), so their degradation in the water column was limited due to their lower bioavailability. It was also observed that sorption to the particulate phase was more intense for longer homologs/ethoxymers for all surfactants. With respect to surface sediments, AES levels were considerably below (<0.25 mg/kg) the values detected for LAS and NPEOs. Concentrations of AEOs, however, were occasionally higher (several tens of ppm) than those found for the rest of the target compounds in several sampling stations.     

Effects of long-term soil amendment with sewage sludges on soil humic acid thermal and molecular properties

Sewage sludges are frequently used as soil amendments due to their high contents of organic matter and nutrients, particularly N and P. However, their effects upon the chemistry of soil humic acids, one of the main components of the soil organic matter, need to be more deeply studied in order to understand the relation between organic matter structure and beneficial soil properties. Two sewage sludges subjected to different types of pre-treatment (composted and thermally dried) with very different chemical compositions were applied for three consecutive years to an agricultural soil under long-term field study. Thermal analysis (TG–DTG–DTA) and solid-state ¹³C NMR spectroscopy were used to compare molecular and structural properties of humic acids isolated from sewage sludges, and to determine changes in amended soils. Thermally dried sewage sludge humic acids showed an important presence of alkyl and O/N-alkyl compounds (70%) while composted sludge humic acids comprised 50% aromatic and carbonyl carbon. In spite of important differences in the initial chemical and thermal properties of the two types of sewage sludges, the chemical and thermal properties of the soil humic acids were quite similar to one another after 3 years of amendment. Long-term application of both sewage sludges resulted in 80–90% enrichment in alkyl carbon and organic nitrogen contents of the soil humic acid fraction.