PCDD/Fs and DL-PCBs in feeding fats obtained as co-products or by-products derived from the food chain

Among the tasks included in the "Quality and safety of feeding fats obtained from co-products or by-products of the food chain" Project, supported by the European Union and included in the 6th Framework Program, a number of fats and oils collected as co- or by-products from the food chain were selected for the determination of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and 'dioxin-like' polychlorinated biphenyls (DL-PCBs). In the majority of the cases these samples are currently employed as feed ingredients. Nevertheless, additional fats, which are forbidden for feedstuff purposes were also considered in this study. In general terms, fats and oils were classified taking into account their nature and the processes applied to obtain these co- or by-products. PCDD/F and DL-PCB levels were evaluated in a first group of samples composed of fish oils, animal fats and lecithins. As expected, fats and oils with an animal origin presented higher concentrations, expressed in pg WHO-TEQ/g, compared to the levels found in vegetable samples like lecithins. The category of fish oils had the highest values for both PCDD/Fs and the sum of PCDD/Fs and DL-PCBs, with some samples showing levels above the maximum established at the present legislation related to the presence of PCDD/Fs and DL-PCBs in animal feed [Commission Directive 2006/13/EC of 3 February 2006 amending Annexes I and II to Directive 2002/32/EC of the European Parliament and of the Council on undesirable substances in animal feed as regards dioxins and dioxin-like PCBs. Official Journal of the European Communities L32, 44-53]. In a second group, fats and oils with a more complex composition obtained from different transformation processes or even mixtures of fats were considered; thus, acid oils from chemical refining, acid oils from physical refining, recycled cooking oils, oils extracted from exhausted bleaching earths, hydrogenated by-products, fatty acids calcium soaps and miscellaneous fats were analyzed. The data revealed a significant variability in PCDD/F and DL-PCB levels, expressed in pg WHO-TEQ/g, in these products. It has to be pointed out that the analyses of fats and oils belonging to these categories of products were sometimes difficult due to the complexity of the samples. In terms of legislation most of these samples cannot be easily included into one of the specific categories of substances intended for feedstuff purposes that are regulated in Commission Directive 2006/13/EC.     

Effect of gas composition in Chemical-Looping Combustion with copper-based oxygen carriers: Fate of sulphur

Chemical-Looping Combustion (CLC) is an emerging technology for CO₂ capture because separation of this gas from the other flue gas components is inherent to the process and thus no energy is expended for the separation. Natural or refinery gas can be used as gaseous fuels and they may contain different amounts of sulphur compounds, such as H₂S and COS. This paper presents the combustion results obtained with a Cu-based oxygen carrier using mixtures of CH₄ and H₂S as fuel. The influence of H₂S concentration on the gas product distribution and combustion efficiency, sulphur splitting between the fuel reactor (FR) and the air reactor (AR), oxygen carrier deactivation and material agglomeration was investigated in a continuous CLC plant (500 W_th). The oxygen carrier to fuel ratio, ?, was the main operating parameter affecting the CLC system. Complete fuel combustion were reached at 1073 K working at ? values ≥1.5. The presence of H₂S did not produce a decrease in the combustion efficiency even when working with a fuel containing 1300 vppm H₂S. At these conditions, the great majority of the sulphur fed into the system was released in the gas outlet of the FR as SO₂, affecting to the quality of the CO₂ produced. Formation of copper sulphide, Cu₂S, and the subsequent reactivity loss was only detected working at low values of ? ≤ 1.5, although this fact did not produce any agglomeration problem in the fluidized beds. In addition, the oxygen carrier was fully regenerated in a H₂S-free environment. It can be concluded that Cu-based oxygen carriers are adequate materials to be used in a CLC process using fuels containing H₂S although quality of the CO₂ produced is affected.     

Priority organic pollutant assessment of sludges for agricultural purposes

A comprehensive characterization of five of the seven priority organic pollutants listed in the draft of the "Working document on sludge" [EU, 2000. Working Document on Sludge 3rd Draft. Unpublished, 19 p] has been carried out during 2001-2003 in sludge samples from Catalonia (NE Spain). One hundred and thirty-nine samples belonging to 20 Waste Water Treatment Plants (WWTPs), seven sludge treatment (thermal drying) and three composting sludge plants were taken in order to determine the concentration of polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs), di-2-(ethyl-hexyl)-phthalate (DEHP), nonylphenol and nonylphenol ethoxylates with one or two ethoxy groups (NPE), polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). PCDD/F concentrations were in general lower than the 100 ng I-TEQ/kg limit suggested in the above-mentioned document. In the same way, 98.5% for PCBs, 97% for PAH and 92.8% for DEHP of the samples presented concentrations lower than 0.8 mg/kg dm, 6 mg/kg dm and 100 mg/kg dm, respectively. In contrast, the vast majority of samples contained NPE concentrations much higher than 50mg/kg dm limit. The values ranged from 14.3 to 3150 mg/kg dm (median value=286.6 mg/kg) being composted sludge samples the less contaminated ones (17.9-363.4 mg/kg dm; median value=89.3 mg/kg). Special attention should be paid to the Catalan sludge NPE contamination owing to the high levels detected.     

Surveillance programme on dioxin levels in ambient air sites in Catalonia (Spain)

As part of a survey programme conducted by the Environment Department of the Autonomous Government of Catalonia in collaboration with the Spanish Council for Scientific Research (CSIC), dioxin concentrations in ambient air were measured in the four provinces of Catalonia (Spain). The study was also performed with the intention of providing data as a basis for future monitoring and evaluation of temporal trends in ambient air. Thus, 91 samples were collected in 25 different sites (rural, urban, suburban and industrial) between 1994 and 2000. The levels revealed a variable content of PCDDs/PCDFs depending both on the area and the contamination source. In particular, industrial areas presented levels ranging from 18 to 954 fg I-TEQ/m3. However, findings in urban and suburban sites varied between 13 and 357 fg I-TEQ/m3. As expected, the lowest levels were found in rural areas with levels between 5 and 125 fg I-TEQ/m3.     

An episode of dioxin contamination in feedingstuff: the choline chloride case

In 2000, as part of a survey programme, the German authorities detected high levels of dioxins in a choline chloride (CC) premix used as animal food component. The contaminated additive consisted of different products of mineral and vegetable origin acting as a carrier. The CC was manufactured in Belgium. The final product was produced in and distributed from a plant in Spain. The German authorities informed all European Community members of the incident. The Spanish Ministry of Agriculture, Fisheries and Food and the Regional Authorities immediately conducted a survey in collaboration with the Spanish Council for Scientific Research (CSIC) to determine and isolate the source of the contamination. Analysis of a large number of samples of pure CC, pine sawdust, almond shell and other substances currently used in the preparation of the premix confirmed the presence of a significant amount of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans in mixtures in which pine sawdust was present. An analysis of the congener profiles revealed similarities with those found in technical pentachlorophenol (PCP) formulations. The conclusion was that PCP-contaminated sawdust as carrier for CC was source of dioxin contamination in feedingstuff.     

Green examination: integration of technology for sustainability

The recent development of infrastructure all around the world has resulted in an increasing trend of online examination in universities. The paper is an approach in theory and practical aimed at analyzing the feasibility of sustainable examination in four universities and its environmental impact reducing the paper use terming it as green examination. The paper studied the integration of sustainability through the use of computers and technology in the examination of the universities viz. King Khalid University (KKU), Saudi Arabia, Integral University (IU), India, Aligarh Muslim University (AMU), India, and The Hague University (HU), The Netherlands. The study has analyzed the trend of paper requirement, paper utilized and paper wasted in all the four universities. The environmental impact resulting from reduced paper use has been also analyzed. The feasibility of e-examination, its implementation and the implications has been undertaken in the study. The study concludes that the e-examination can almost make the examinations paperless and feasible in the four universities.     

Dioxin emissions from thermal waste management in Medellín, Colombia: present regulation status and preliminary results

Preliminary results of a study undertaken to characterize dioxin and furan releases from waste incineration plants operating in Medellín-Colombia are presented. Emission and fly ash samples were collected from representative plants burning medical and industrial residues to characterize PCDD/PCDF levels. Analyses were carried out following European standards for stationary gas emissions EN-1948:1996 and US EPA 1613 (fly ashes). Final extracts were analyzed by both high resolution gas chromatography coupled to high resolution mass spectrometry (HRGC-HRMS) and high resolution gas chromatography coupled to ion trap tandem mass spectrometry (HRGC-ITMS/MS). Preliminary results revealed emission levels of 1-30.3 ng I-TEQ/Nm3 depending on whether or not an air pollution control system (APCS) was installed. Fly ashes contained 8.5-68 ng I-TEQ/g. Critical issues that should be addressed in an assessment and in developing waste management plans in Colombia are discussed.     

Decontamination trends in the aquacultured fish gilthead seabream (Sparus aurata) after feeding long-term a PCDD/F spiked feed

Aquacultured fish gilthead seabream (Sparusaurata), previously exposed to low levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) trough the diet for a 13 months period, were fed on a clean feed for another 22 months. Gilthead seabream is a protandrous hermaphrodite species and this “decontamination” period coincided with the stages of sex differentiation, maturity and reproduction of the fish. PCDD/F levels in the fish tissues (i.e. muscle, liver, perivisceral fat and gonads), expressed in pg WHO-TEQ g⁻¹ fresh weight, showed a general decreasing trend during the “decontamination” period. However, this general trend varied among tissues and was also dependent on sex and lipid contents. Toxicological effects affecting fish behaviour and hepatic marker responses were also evaluated. The results pointed out that exposure to PCDD/Fs did not have an impact on fish development and reproduction, since the proportion of sexes found after the sex reversal process was within the normal range described for this species. In addition, long-term exposure to low PCDD/F levels did not significantly affect the response of most of the biochemical markers considered. On the contrary, some of them (e.g. EROD activity) showed variations in their responses during the sex differentiation process and onwards. Finally, the hepatic AhR mRNA levels increased during dioxin exposure but they returned to values typical for non-exposed fish after the “decontamination” period.     

Assessment of polychlorinated dibenzo-p-dioxin and dibenzofuran emissions from a hazardous waste incineration plant using long-term sampling equipment

The aim of this work is to evaluate the performance of a continuous monitoring system for the analysis of the mass concentration of PCDD/Fs from stationary sources. Data was acquired from a modern, state of the art, hazardous waste thermal treatment plant for a period of more than 2 years using a commercial available continuous monitoring system. The study consisted of a total of 16 samples, collected in periods from 1 week to 2 months resulting in an average of 360 m³ sampled flue gas per sample. The study showed the system was able to confirm that for a period of more than 2 years the plant was complying with the limit of 0.1 ng I-TEQ/Nm³. In addition, the data showed the typical fingerprint of such installations which is useful for example in impact studies. Long-term samples were compared to five short-term samples (6 h) collected every 6 months during the study period. Principal component analysis was applied to PCDD/Fs obtained data as useful statistical tool to find out trends and similarities between different samples. Improvement in terms of representativeness of data was achieved through continuous assessment since the starts of the project. The obtained data was further used to determine the emission factor for this activity and the total annual PCDD/Fs release to the atmosphere.