Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part I. Application to surface, waste and indirect discharge water samples in Austria

A method for simultaneous quantitative determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds (QACs) has been developed, validated and subsequently applied to real water samples in Austria. The method employs liquid-liquid extraction (LLE) followed by liquid chromatography/tandem mass spectrometry (LC-MS/MS), using electrospray ionization (ESI) in positive mode. The overall method quantification limits range from 4 to 19ng/L for the enrichment of 500mL water samples and analyte recoveries are between 80 and 99%. The method was applied to 62 of the respective water samples without filtration to avoid the loss of the analytes due to the high adsorption capacity of these compounds. Maxima in the mg/L range, especially in the wastewater of hospitals and laundries, could be detected for the selected target compounds.     

Estrogenic activity associated with organochlorine compounds in fish extracts from European mountain lakes

Fish muscle extracts from ten European mountain lakes were analyzed for organochlorine compounds (OCs) and estrogenic activity, the latter by a recombinant yeast assay based on the human estrogen receptor. Seventy percent of the samples showed estrogenic activity above detection limits and a subset of five samples showed estrogenic activities, equivalent to more than 10,000 pg/g of estradiol. These highly estrogenic samples occurred in two lakes, Velké Hin?ovo in the Tatra Mountains and Redon in the Pyrenees. Principal component analysis correlated estrogenic activity of muscle extracts to fish age and concentrations of the more chlorinated polychlorobiphenyls (PCBs). This is consistent with previously observed correlations of these PCBs with fish age. In addition, most fish with high estrogenic activity were found in lakes containing high OC levels in the sediments, which gives further ground to atmospheric deposition of anthropogenic pollutants as main process leading to the observed endocrine disruption effects.     

On the presence of enriched amounts of 235U in hot particles from the terrestrial area affected by the Palomares accident (Spain)

The characterisation by ICP-MS of an isolated Pu-U hot particle originating from the nuclear weapons accident in Palomares (Spain) shows, for the first time, that its uranium content is highly enriched in (235)U. The enrichment has been confirmed by independent analyses of two surface soil samples collected in a heavily contaminated area close to the impact point of one of the bombs. This finding clarifies better the composition of the weapons involved in the accident and is of importance when the inventory of U and Pu in the contaminated area are to be calculated.     

Pyrolysis of mixtures of sewage sludge and manure: a comparison of the results obtained in the laboratory (semi-pilot) and in a pilot plant

A pilot-scale pyrolysis process was carried out for the treatment of a mixture of two types of waste, sewage sludge and cattle manure, comparing the results with others obtained under laboratory conditions (semi-pilot scale). The aim of this study was to obtain the energetic valorization of the products. Owing to the specific characteristics of the plant, two products were obtained from the process: gas and carbonized solid. As no liquid fraction was obtained, the gas fraction is a greater percentage made up of both condensable and non-condensable compounds, which were obtained separately at the laboratory scale. The pilot plant was designed so that the gases produced by thermolysis were burnt continuously in a combustion chamber, while the carbonized fraction was fed in batches for co-combustion. To determine composition and combustion ability, the gas and solid products from the pilot process were characterized by chromatographic analysis of the gaseous fraction and chemical analysis and programmed-temperature combustion of the carbonized solid. The composition of the combustion gases, rich in light hydrocarbons, and the carbon present in the carbonized fraction enable the energetic valorization of these products. The combustion gases were subjected to a cleaning process and their composition analysed twice: before and after the gas cleaning treatment. The study led to a positive assessment of the possible use of the process products as fuel, provided that the combustion gases are treated. As most of the sulphur and chlorine from the original waste are mainly concentrated in the solid fraction, the use of char as a fuel will depend on the effectiveness of clean-up techniques for combustion gases. During gas cleansing, neutralizing with sodium bicarbonate proved effective, especially for the acidic compounds HCl, HF and SO(2).     

Chemical and biological characterization of slaughterhouse wastes compost

The chemical and biological properties of compost made from yard trimmings (YT) composted alone or mixed with slaughterhouse wastes (SHW) were evaluated in seven phases. Mixtures were weighed in a 2:1 proportion (YT:SHW) and placed in composting bins (0.91 m2). Temperature was recorded to determine the time (d) needed to reach the first (1HC) and second heat cycles (2HC). Composting characteristics were measured at 0 d, at the peak of the 1HC and 2HC, and at maturation (0, 20, 50 and 70 d). During 1HC, bacterial isolates were cultivated in both treatments and identified using the Biolog System. Chemical composition was statistically analyzed using a 2 (layers of SHW)x7 (composting phases) factorial arrangement of treatments with the ANOVA procedure of SAS. The pH was neutral for YT and ranged from 7.41 to 6.82 for SHW throughout the process. There was a decrease in organic matter (OM) and carbon (C), and a relative increase in nitrogen (N) in both treatments. At 70 d of maturation, C:N values were similar between treatments, but lower (P>0.05) than the initial values. Final N concentration was higher (P>0.05) for the treatment with SHW. Only the SHW treatment exhibited thermophilic temperatures. At the 1HC in both treatments, different populations of bacteria responsible for the breakdown of OM were identified showing an active heterogeneous population. The presence of pathogenic microorganisms was not detected in treatments containing SHW.     

Management of MSW in Spain and recovery of packaging steel scrap

Packaging steel is more advantageously recovered and recycled than other packaging material due to its magnetic properties. The steel used for packaging is of high quality, and post-consumer waste therefore produces high-grade ferrous scrap. Recycling is thus an important issue for reducing raw material consumption, including iron ore, coal and energy. Household refuse management consists of collection/disposal, transport, and processing and treatment - incineration and composting being the most widely used methods in Spain. Total Spanish MSW production exceeds 21 million tons per year, of which 28.1% and 6.2% are treated in compost and incineration plants, respectively. This paper presents a comprehensive study of incineration and compost plants in Spain, including a review of the different processes and technologies employed and the characteristics and quality of the recovered ferrous scrap. Of the total amount of packaging steel scrap recovered from MSW, 38% comes from compost plants and 14% from incineration plants. Ferrous scrap from incineration plants presents a high degree of chemical alteration as a consequence of the thermal process to which the MSW is subjected, particularly the conditions in which the slag is cooled, and accordingly its quality diminishes. Fragmentation and magnetic separation processes produce an enhancement of the scrap quality. Ferrous scrap from compost plants has a high tin content, which negatively affects its recycling. Cleaning and detinning processes are required prior to recycling.     

Effects of sewage sludge blending on the coal combustion: a thermogravimetric assessment

Combustion of urban sewage sludge together with coal in existing infrastructures may be a sustainable management option energetically interesting for these materials, usually considered wastes. Thermogravimetric analysis was used to study the combustion of a semianthracite coal and the modifications undergone when adding a small percentage (2%, 5%, 10%) of sewage sludge. Both Differential Scanning Calorimetric analysis and Differential Thermogravimetry burning profiles showed differences between coal and sewage sludge combustion. However, the effects of adding a percentage of sewage sludge equal or smaller than 10% was hardly noticeable in terms of heat release and weight loss during the coal combustion. This was further proved by non-isothermal kinetic analysis, which was used to evaluate the Arrhenius activation energy corresponding to the co-combustion of the blends. This work shows that thermogravimetric analysis may be used as an easy rapid tool to asses the co-combustion of sewage sludge together with coal.     

Integrated catalytic wet air oxidation and aerobic biological treatment in a municipal WWTP of a high-strength o-cresol wastewater

This study examines the feasibility of coupling a Catalytic Wet Air Oxidation (CWAO), with activated carbon (AC) as catalyst, and an aerobic biological treatment to treat a high-strength o-cresol wastewater. Two goals are pursued: (a) To determine the effect of the main AC/CWAO intermediates on the activated sludge of a municipal WasteWater Treatment Plant (WWTP) and (b) To demonstrate the feasibility of coupling the AC/CWAO effluent as a part of the influent of a municipal WWTP. In a previous study, a high-strength o-cresol wastewater was treated by AC/CWAO aiming to establish the distribution of intermediates and the biodegradability enhancement. In this work, the biodegradability, toxicity and inhibition of the most relevant intermediates detected in the AC/CWAO effluent were determined by respirometry. Also, the results of a pilot scale municipal WWTP study for an integrated AC/CWAO-aerobic biological treatment of this effluent are presented. The biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) of main AC/CWAO intermediates allowed the classification of the intermediates into readily biodegradable, inert or toxic/inhibitory compounds. This detailed study, allowed to understand the biodegradability enhancement exhibited by an AC/CWAO effluent and to achieve a successful strategy for coupling the AC/CWAO step with an aerobic biological treatment for a high-strength o-cresol wastewater. Using 30%, as COD, of AC/CWAO effluent in the inlet to the pilot scale WWTP, the integrated AC/CWAO-biological treatment achieved a 98% of total COD removal and, particularly, a 91% of AC/CWAO effluent COD removal without any undesirable effect on the biomass.     

Seasonal variations of selected herbicides and related metabolites in water, sediment, seaweed and clams in the Sacca di Goro coastal lagoon (Northern Adriatic)

This study assesses the status of Sacca di Goro coastal lagoon (Northern Adriatic, Italy) with respect to watershed pollution. Because 80% of its watershed is devoted to agriculture, plant protection products and their metabolites were found in the water column, sediments (the upper 0-15 cm layer), macroalgae (Ulva rigida) and clams (Tapes philippinarum). Five seasonal sampling campaigns were performed from May 2004 to April 2005 and concentrations measured in five stations in the lagoon and six in the watershed. Relatively high concentrations of the s-triazine - terbuthylazine -, urea herbicides - diuron - and alachlor were detected through the year mainly at stations directly influenced by the Po di Volano inflow. The concentrations of products in use follow a clear seasonal pattern with spring peaks. This pattern is also visible in the sediments as well as in biota. Among metabolites, hydroxylated compounds prevailed, often with concentrations greater than those of the parent compounds. For the most part of the year, the concentrations in biota were close to detection limits, with concentration peaks in spring.     

Evaluation of natural and anthropogenic influences on the Guadalquivir River (Spain) by dissolved heavy metals and nutrients

To evaluate both the natural and anthropogenic influences on surface waters of Guadalquivir River (SW-Spain), concentrations of dissolved trace metals (Mn, Co, Ni, Cu, Cd, Zn, and Pb), inorganic nutrients (N-NH(4)(+), N-NO(3)(-), N-NO(2)(-), and P-PO(4)(3-)) and other variables as conductivity, pH, dissolved oxygen (DO) and suspended solids (SS) were measured during a three-years period (2001-2003). Samples were taken at 26 stations twice a year, during rain and dry periods. The analysis of variance (ANOVA) suggested that temporal variations within the period of study were statistically negligible. Spatial distributions identified three different zones, mainly influenced by sewage (Eastern Zone), agriculture runoffs (Central Zone), and estuarine processes (Western Zone), respectively. Principal Component and Cluster Analysis allowed to identify the variables controlling the water quality of each zone as: N-NH(4)(+), N-NO(2)(-), Mn, and Co, (Eastern Zone), SS, and P-PO(4)(3-) (Central Zone), and Cd, pH and conductivity (Western Zone). Other variables such as Ni, Cu, Zn or N-NO(3)(-), influenced two different zones, while Pb presented a singular behavior.