ESF Workshop

Dioxin and PCB monitoring programs for food and feeding stuff in most countries of the world, including many European Countries are currently inadequate. Better control of food production lines and food processing procedures is needed to minimize entry of dioxin to the food chain and will help to avoid dioxin contamination accidents. This would also improve the ability to trace back a possible contamination to its source. European guidelines for monitoring programs should be established to ensure comparable and meaningful results. These guidelines should define the minimum requirements for the design of monitoring programs, analytical methods, and quality assurance. Though data from Northern Europe shows that the general population exposure to dioxin and PCB has decreased during the last ten years these compounds continue to be a risk of accidental contamination of the food chain. The most prominent recent example is the Belgian dioxin contamination of feeding stuff in 1999. The Belgian dioxin contamination was not detected due to dioxin monitoring programs but by their direct biological effects seen in animals. Four other cases of dioxin contamination have been detected in Europe since 1997 due to local monitoring programs. One of them (citrus pulp pellets 1998) was in a much larger scale than the Belgian dioxin contamination. The general population's exposure to dioxins and PCBs is still in the same range (1-4 pg WHO-TEQ/kg body weight and day) as the recently revised WHO tolerable daily intake (TDI). There is concern that short-term high level exposure to dioxins, furans, and PCB may cause biological effects on the human fetal development and further research is required. Further actions to control sources building on considerable advances already made in many countries may need to be supplemented by measures to prevent direct contamination of feeding stuff or food to reduce general population exposure further.     

Application of a purge and trap TDS-GC/MS procedure for the determination of emissions from flame retarded polymers

Emissions of volatile organic compounds (VOCs) from different thermoplastic polymers used in electrotechnical applications were investigated using a purge and trap procedure that involved adsorption on Tenax GR. Results were compared to those for an operating TV set monitored in a test chamber. The analyses were in both cases carried out using thermodesorption gas chromatography with mass spectrometric detection (TDS-GC/MS). Substances identified were monomers, volatile additives, or related compounds. Special attention was given to the detection of halogenated compounds. Their origin was studied using reference samples and synthetic standards.     

Monitoring, modelling and environmental exposure assessment of industrial chemicals in the aquatic environment

Monitoring and laboratory data play integral roles alongside fate and exposure models in comprehensive risk assessments. The principle in the European Union Technical Guidance Documents for risk assessment is that measured data may take precedence over model results but only after they are judged to be of adequate reliability and to be representative of the particular environmental compartments to which they are applied. In practice, laboratory and field data are used to provide parameters for the models, while monitoring data are used to validate the models' predictions. Thus, comprehensive risk assessments require the integration of laboratory and monitoring data with the model predictions. However, this interplay is often overlooked. Discrepancies between the results of models and monitoring should be investigated in terms of the representativeness of both. Certainly, in the context of the EU risk assessment of existing chemicals, the specific requirements for monitoring data have not been adequately addressed. The resources required for environmental monitoring, both in terms of manpower and equipment, can be very significant. The design of monitoring programmes to optimise the use of resources and the use of models as a cost-effective alternative are increasing in importance. Generic considerations and criteria for the design of new monitoring programmes to generate representative quality data for the aquatic compartment are outlined and the criteria for the use of existing data are discussed. In particular, there is a need to improve the accessibility to data sets, to standardise the data sets, to promote communication and harmonisation of programmes and to incorporate the flexibility to change monitoring protocols to amend the chemicals under investigation in line with changing needs and priorities.     

Nitrogen recovery in an integrated system for wastewater treatment and tilapia production

An integrated system, consisting of Up-flow Anaerobic Sludge Blanket (UASB)-duckweed-tilapia ponds was used for recovery of sewage nutrients and water recycling. A UASB reactor with 40 liter working volume was used as pre-treatment unit followed by a series of three duckweed ponds for nitrogen recovery. The treated effluent and duckweed biomass was used to feed fishponds stocked with Nile tilapia (Oreochromis niloticus). The UASB reactor was fed with raw, domestic sewage at 6 h hydraulic retention time. The three duckweed ponds were stocked with Lemna gibba and fed with UASB effluent at 15 days hydraulic retention time. Nitrogen recovery from UASB effluent via duckweed biomass represented 81% of total nitrogen removal and 46.5% from the total nitrogen input to the system. In subsequent fishponds the nitrogen recovery from duckweed as fish feed was in the range of 13.4–20%. This nitrogen in fish biomass represented 10.6–11.5 g N from the total nitrogen in the raw sewage fed to the UASB reactor. The growth performance of tilapia (Oreochromis niloticus) showed specific growth rates (SGR) in the range of 0.53–0.97. The range of feed conversion ratio (FCR) and protein efficiency ratio (PER) were 1.2–2.2 and 2.1–2.28, respectively. The results of the experiments showed total fish yield and net fish yield in the range of 17–22.8 ton/ha/y and 11.8–15.7 ton/ha/y respectively. In conclusion UASB-duckweed-tilapia ponds provide marketable by-products in the form of duckweed and fish protein, which represent a cost recovery for sewage treatment.     

Fish bioassay monitoring of waste effluents

Spills of toxic materials into bodies of water receiving industrial waste discharges can be prevented only if frequent or continuous assessments of effluent quality can be made. Currently available methods can automatically measure individual physical or chemical waste components but cannot assess toxicity caused by the interaction of components or the presence of an unsuspected material. Aquatic organisms, in contrast, respond to their total environment and in this way integrate the effects of all the various chemical and physical waste parameters.This study evaluates the possibility of using the continuously and automatically recorded responses of fish to monitor the toxicity of industrial waste effluents. A review of previously developed toxicity monitoring systems is followed by a field evaluation of a method that uses the computer-monitored ventilatory patterns of 12 bluegills (Lepomis macrochirus Rafinesque) to monitor the toxicity of an industrial waste effluent as it flows into a river. No known toxic spills occurred in the effluent during the operation of this system, but acetone added to the effluent waste caused responses from the fish at concentrations which peaked near the 96-hr LC₅₀ level. Some responses were also noted when no known toxicant was present; these were related to environmental disturbances and system design problems. Recommendations are made for the design of future biologic monitoring units.     

Mass Spectrometric Detection and Identification of Polar Pesticides and their Degradation Products - A Comparison of Different Ionization Methods

Due to increasing use of polar pesticides, they are found together with their degradation products in ground- and surface waters serving for drinking water treatment. The triazine derivatives acetamido-atrazine, ametryne, atrazine, cyanazine, deethylatrazine, deethyldeisopropyl-hydroxyatrazine, deethyl-hydroxyatrazine, deisopropyl-atrazin, deisopropyl-hydroxyatrazine, desmetryn, hydroxyatrazine, prometryne, propazine, simazine, terbumeton, terbutryne and terbutylazine, and the pesticides 2,4-D, dichlorprop, isoproturon, diuron, metolachlor, glyphosate, metsulfuronmethyl and dalapon, all of them belonging to this type of pesticides, have been studied. For determination of triazine derivatives UV detection by means of diode array detector (DAD) as well as mass spectrometric (MS) detection coupled by thermospray interface (TSP) have been used successfully after liquid chromatoraphic (LC) separation. Interfaces like thermospray (TSP), electrospray (ESP) and atmospheric pressure chemical ionisation (APCI) were examined with regard to their suitability for substance-specific detection of polar pesticides by flow injection analysis (FIA) with MS- and tandem mass spectroscopic detection (MS/MS) without preceding LC separation. Optimised detection conditions for these pesticides using FIA are presented, and solutions for occurring problems are offered.     

The stable isotope signature of methane emitted from plant material under UV irradiation

Recent experiments have shown that dry and fresh leaves, other plant matter, as well as several structural plant components, emit methane upon irradiation with UV light. Here we present the source isotope signatures of the methane emitted from a range of dry natural plant leaves and structural compounds. UV-induced methane from organic matter is strongly depleted in both ¹³C and D compared to the bulk biomass. The isotopic content of plant methoxyl groups, which have been identified as important precursors of aerobic methane formation in plants, falls roughly halfway between the bulk and CH₄ isotopic composition. C3 and C4/CAM plants show the well-established isotope difference in bulk ¹³C content. Our results show that they also emit CH₄ with different δ¹³C value. Furthermore, δ¹³C of methoxyl groups in the plant material, and ester methoxyl groups only, show a similar difference between C3 and C4/CAM plants. The correlation between the δ¹³C of emitted CH₄ and methoxyl groups implies that methoxyl groups are not the only source substrate of CH₄.Interestingly, δD values of the emitted CH₄ are also found to be different for C3 and C4 plants, although there is no significant difference in the bulk material. Bulk δD analyses may be compromised by a large reservoir of exchangeable hydrogen, but no significant δD difference is found either for the methoxyl groups, which do not contain exchangeable hydrogen. The δD difference in CH₄ between C3 and C4 plants indicates that at least two different reservoirs are involved in CH₄ emission. One of them is the OCH₃ group, the other one must be significantly depleted, and contribute more to the emissions of C3 plants compared to C4 plants. In qualitative agreement with this hypothesis, CH₄ emission rates are higher for C3 plants than for C4 plants.     

Effect of Macroalgal Expansion and Marine Protected Areas on Coral Recovery Following a Climatic Disturbance

Disturbance plays an important role in structuring marine ecosystems, and there is a need to understand how conservation practices, such as the designation of Marine Protected Areas (MPAs), facilitate postdisturbance recovery. We evaluated the association of MPAs, herbivorous fish biomass, substrate type, postdisturbance coral cover, and change in macroalgal cover with coral recovery on the fringing reefs of the inner Seychelle islands, where coral mortality after a 1998 bleaching event was extensive. We visually estimated benthic cover and fish biomass at 9 sites in MPAs where fishing is banned and at 12 sites where fishing is permitted in 1994, 2005, 2008, and 2011. We used analysis of variance to examine spatial and temporal variations in coral cover and generalized additive models to identify relations between coral recovery and the aforementioned factors that may promote recovery. Coral recovery occurred on all substrate types, but it was highly variable among sites and times. Between 2005 and 2011 the increase in coral cover averaged 1%/year across 21 sites, and the maximum increase was 4%/year. However, mean coral cover across the study area (14%) remained at half of 1994 levels (28%). Sites within MPAs had faster rates of coral recovery than sites in fished areas only where cover of macroalgae was low and had not increased over time. In MPAs where macroalgae cover expanded since 1998 there was no recovery. Where coral was recovering on granite reefs there was a shift in relative prevalence of colony life‐form from branching to encrusting species. This simplification of reef structure may affect associated reef fauna even if predisturbance levels of coral cover are attained. Efecto de la Expansión de Macroalgas y Áreas Marinas Protegidas sobre la Recuperación de Coral Después de una Perturbación Climática