Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'(W)) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb(T)) in pure water. Experimental breakthrough volumes (Vb(E)) were first determined using purified and deionized water as the matrix for selected compounds having Vb(T) < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4-5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb(E) curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5-6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb(E) in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.     

Co-treatment of hydrogen sulfide and methanol in a single-stage biotrickling filter under acidic conditions

Biofiltration of waste gases is cost-effective and environment-friendly compared to the conventional techniques for treating large flow rates of gas streams with low concentrations of pollutants. Pulp and paper industry off-gases usually contain reduced sulfur compounds, such as hydrogen sulfide and a wide range of volatile organic compounds (VOCs), e.g., methanol. It is desirable to eliminate both of these groups of compounds. Since the co-treatment of inorganic sulfur compounds and VOCs in biotrickling filters is a relatively unexplored area, the simultaneous biotreatment of H2S and methanol as the model VOC was investigated. The results showed that, after adaptation, the elimination capacity of methanol could reach around 236 g m(-3) h(-1) with the simultaneous complete removal (100%) of 12 ppm H2S when the empty bed residence time is 24 s. The pH of the system was around 2. Methanol removal was hardly affected by the presence of hydrogen sulfide, despite the low pH. Conversely, the presence of the VOC in the waste gas reduced the efficiency of H2S biodegradation. The maximal methanol removal decreased somewhat when increasing the gas flow rate. This is the first report on the degradation of methanol at such low pH in a biotrickling filter and on the co-treatment of H2S and VOCs under such conditions.     

Structure of Mn-Zr mixed oxides catalysts and their catalytic performance in the gas-phase oxidation of chlorocarbons

The catalytic activity and selectivity of manganese zirconia mixed oxides were evaluated for the oxidation of two common chlorinated pollutants found in waste streams, namely 1,2-dichloroethane (DCE) and trichloroethylene (TCE). Mixed oxides with varying Mn-Zr content were prepared by coprecipitation via nitrates, and subsequent calcination at 600 degrees C for 4 h in air. These catalysts were characterised by means of several techniques such as atomic emission spectrometry, N2 adsorption-desorption, powder X-ray diffraction, temperature-programmed desorption of ammonia, pyridine adsorption followed by diffuse reflectance infrared spectroscopy and temperature-programmed reduction with hydrogen. The active catalytic behaviour of Mn-Zr mixed oxides was ascribed to a substantial surface acidity combined with readily accessible active oxygen species. Hence, the mixed oxide with 40 mol% manganese content was found to be an optimum catalyst for the combustion of both chlorocarbons with a T50 value around 305 and 315 degrees C for DCE and TCE oxidation, respectively. The major oxidation products were carbon dioxide, hydrogen chloride and chlorine. It was observed that the formation of both CO2 and Cl2 was promoted with Mn loading.     

Trends in background levels of persistent organic pollutants at Kosetice observatory, Czech Republic.2) Part II. Aquatic and terrestrial environments 1996-2005

A multimedia sampling of ambient air, wet deposition, surface water, sediment, soil and biota has been performed at Kosetice background observatory in the southern Czech Republic since 1988. An integrated monitoring approach was applied to assess the current state, anthropogenic impacts, and possible future changes of terrestrial and freshwater environments. Average PCB concentrations in the individual matrices calculated from ten years of sampling on multiple sites varied between 2 ng g(-1) in sediment and 7 ng g(-1) in soil or moss. DDT concentrations were lower in moss and needles (2 ng g(-1) and 4 ng g(-1), respectively) than in sediment (11 ng g(-1)) and soil (20 ng g(-1)), while the HCH level was higher in moss and needles (5 ng g(-1) and 6 ng g(-1), respectively) than in soil or sediment (1 ng g(-1) and 2 ng g(-1), respectively). The highest average level of PAHs was found in soil (600 ng g(-1)), while it was lower in needles (230 ng g(-1)), moss (210 ng g(-1)) or sediment (210 ng g(-1)). Time related trends of concentration levels of persistent organic pollutants in all matrices were investigated. Moss and needle trend patterns resembled those of the ambient air, showing a slight concentration decrease of all compounds, except for hexachlorobenzene. The soil, water and sediment concentrations showed a similar decrease of PAHs, PCBs, and HCHs, but there was no clear trend for DDTs and HCB.     

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.