Introducing an integrated climate change perspective in POPs modelling, monitoring and regulation

This paper presents a review on the implications of climate change on the monitoring, modelling and regulation of persistent organic pollutants (POPs). Current research gaps are also identified and discussed.Long-term data sets are essential to identify relationships between climate fluctuations and changes in chemical species distribution. Reconstructing the influence of climatic changes on POPs environmental behaviour is very challenging in some local studies, and some insights can be obtained by the few available dated sediment cores or by studying POPs response to inter-annual climate fluctuations. Knowledge gaps and future projections can be studied by developing and applying various modelling tools, identifying compounds susceptibility to climate change, local and global effects, orienting international policies.Long-term monitoring strategies and modelling exercises taking into account climate change should be considered when devising new regulatory plans in chemicals management.     

Economic assessment of managing processionary moth in pine forests: a case-study in Portugal

This paper assesses the private and social profitability of current strategies for managing processionary moth (Thaumetopoea pityocampa) in Portuguese pine forests, looking at economic and environmental costs and benefits. Costs include the expenses for forest treatment and the social costs of threats to human health (dermatitis amongst others); benefits are assessed in terms of both revenue and social benefits such as carbon fixation and recreation. The evaluation was done using Cost Benefit Analysis (CBA) as an analytical framework. While this tool is currently applied to forest and environmental assessment and specific applications to pest management strategies are to be found in agricultural economics, rather few attempts have been made in the field of forest pest management. In order to assess and compare with--without options, a case-study was analysed for the Setúbal Peninsula, south of Lisbon, an area where extensive stands of maritime pine (Pinus pinaster) grow. The exercise has shown that CBA can be a valuable tool for assessing the economic and social profitability of pest management. The results demonstrate that the loss of revenues in the no-management option is not sufficient to make pest management profitable for private forest owners in the short-term. Conversely, a social profit is gained as pest management minimizes health risks for humans and avoids possible recreational losses.     

Speciation of Cr and its leachability in coal by-products from spanish coal combustion plants

This study evaluates the behaviour of total Cr and Cr (VI) during coal combustion in two Spanish power stations. The content and distribution of Cr in the feed coal and combustion wastes was determined and the Cr contents were normalized using enrichment factor indexes. The speciation of Cr in the fly ash fractions from the different hoppers of the electrostatic precipitators was established and the possibility that the Cr (VI) might lixiviate when ashes are disposed of at landfill sites was assessed. Differences in the distribution and behavior of Cr in the two power stations were observed. According to European directive 1999/31/CEE, soluble Cr(VI) in the fly ashes studied would be unlikely to pose an environmental or health risk when the ash is disposed of.     

Growth, photosynthetic and respiratory responses to sub-lethal copper concentrations in Scenedesmus incrassatulus (Chlorophyceae)

In the present paper we investigated the effects of sub-lethal concentrations of Cu²⁺ in the growth and metabolism of Scenedesmus incrassatulus. We found that the effect of Cu²⁺ on growth, photosynthetic pigments (chlorophylls and carotenoids) and metabolism do not follow the same pattern. Photosynthesis was more sensitive than respiration. The analysis of chlorophyll a fluorescence transient shows that the effect of sub-lethal Cu²⁺ concentration in vivo, causes a reduction of the active PSII reaction centers and the primary charge separation, decreasing the quantum yield of PSII, the electron transport rate and the photosynthetic O₂ evolution. The order of sensitivity found was: Growth > photosynthetic pigments content = photosynthetic O₂ evolution > photosynthetic electron transport > respiration. The uncoupled relationship between growth and metabolism is discussed.     

Occurrence of alkylphenolic substances in a Great Lakes coastal marsh, Cootes Paradise, ON, Canada

Occurrence and fate of alkylphenols (APs), known endocrine disruptors, were investigated in a Great Lakes coastal wetland, Cootes Paradise, ON. The wetland, which receives discharges from a Wastewater Treatment Plant (WTP) and several Combined Sewer Overflows (CSOs), is an important spawning ground for fish and crucial habitat for other fauna. Elevated concentrations of nonylphenol ethoxylates (NPEs) and their degradation product nonylphenol (NP) were found in water and sediment samples near the sources. Since transfer of APs through the food chain is of concern, we compared their concentrations in invertebrates from clean and contaminated sites. The results reveal transfer of alkylphenolics from sediments to biota and their accumulation in the invertebrate tissue, particularly the highly hydrophobic 4-NP, whose concentrations ranged from 1.9 to 6.3 microg g(-1). To our knowledge, this is the first study to evaluate AP concentrations in tissue of benthic invertebrates under real environmental conditions.     

Bioremediation process on Brazil shoreline

GOAL, SCOPE AND BACKGROUND: Bioremediation technique can be considered a promising alternative to clean oil spills using microbial processes to reduce the concentration and/or the toxicity of pollutants. To understand the importance of this work we must know that there is only little research performed to date using bioremediation techniques to clean oil spills in tropical countries. So, the main objective of this work is to analyze the behavior of a laboratory's bioremediation test using nutrients on coastal sediments. METHODS: The bioremediation process is followed through geochemical analysis during the tests. This organic material is analyzed by medium pressure liquid chromatography (MPLC), gas chromatography/flame ionization detection (GC/FID) and gas chromatography/ mass spectrometry. By microbial counting, the number of total bacteria and degrading bacteria is determined during the experiments, in order to confirm the effectiveness of the bioremediation process. The seawater obtained throughout the bioremediation process is analyzed for nutrients grade (phosphate and ammonium ions) and also for its toxicity (Microtox tests) due the presence of hydrocarbons and fertilizer. RESULTS: The results from the geochemical analyses of the oil show a relative decrease in the saturated hydrocarbon fraction that is compensated by a relative enrichment on polar compounds. It's confirmed by the fingerprint evaluation where it is possible to see a complete reduction of the normal alkanes followed by isoprenoids. Seawater analysis done by toxicity and nutrients analysis, such as microbial counting (total and degrading bacteria), confirm the fertilizer effectiveness during the bioremediation process. DISCUSSION: Results from simulating test using NPK, a low-price plant fertilizer, suggest that it's able to stimulate the degradation process. Results from medium pressure liquid chromatography (MPLC), done at two different depths (surface and subsurface), show different behavior during the biodegradation process where the later is seen to be more susceptible to microbial attack. Data from bioremediation unit shows a bigger reduction of the saturated fraction, followed by some smaller reduction of aromatic fractions, compensated by a relative increase from polar compounds (NSO). n-C17/pristane, n-C18/ fitane and pristane/fitane rates show constant values for the unity control, different from bioremediation samples which have a significant reduction, especially on subsurface areas, where a strong fall in the rates, seen to be reduced to zero over twenty days, had occurred during the first ten days. However, sample surfaces are reduced to zero in thirty days of experiments, proving that biodegradation is better on subsurfaces. Gaseous chromatography/mass spectrometry (CG/MS) analysis shows constant values to cyclic biomarker rates and aromatic compounds, suggesting that the biodegradation process is not strong enough to reduce these composites. Microbial analysis shows a reduction on heterotrophic (total bacteria) number from control unit, probably because the bacteria uses the spill oil like carbon source and energy. However, the number increases on bioremediation unit, because it uses NPK like a biostimulator. The hydrocarbonoclastic number isn't enough on the first moment, but it's detected after 30 days and quantified in all units, showing big values especially in bioremediation. Toxicity tests confirm that NPK fertilizer does not intoxicate the shoreline during the application of the bioremediation technique. Some nutrient concentration shows high values of ammonium and phosphate per bioremediation unit, reducing by the end of the experiment. CONCLUSIONS: Results reached the goal, finding a proper nutrient (NPK fertilizer) to stimulate the biodegradation process, growing bacteria responsible for reducing impact-contaminated coast ambient by oil spills. Chemical analysis of oil shows a reduction in the saturated fraction with a relative enrichment in polar composites (NSO) and the aromatic fraction from oil remaining constant. Subsurface samples show more biodegradation than surface samples, probably because the first one has higher humidity. Linear alcanes are more biodegraded than isoprenoids, confirming the biodegradation susceptibility order. Saturated cyclic biomarkers and aromatic compounds show constant behavior maybe because the nutrients or time was not enough for microorganismic attack. Fertilizer does not demonstrate any toxic effects in local biota so that it does not compromise the technique applicability and the environment is not saturated by nutrients during the simulation, especially since the coastal environment is an open system affected daily by tides. Therefore, bioremediation tests can be classified as moderate, reaching level 5 in the classification scale by Peters & Moldowan (1993). RECOMMENDATIONS AND PERSPECTIVES: The use of marine environment by the petroleum industry on exploration, production and transportation operation, transform this oil to become the most important pollutant in the oceans. Bioremediation is an important technique used to clean spilled oil impacting on shorelines, accelerating the biodegradation process by using fertilizer growing the microorganisms responsible for decontaminating the environment. We recommend confirming the efficiency of NPK nutrient used on bioremediation simulating experiments on beaches, while monitoring the chemical changes long-term. NPK fertilizer can be used to stimulate the biodegradation process on shoreline impacted by spilled oil.     

Biochemical effects of clomazone herbicide on piava (Leporinus obtusidens)

This study aims to verify the effects of the clomazone concentration used in rice fields on acetylcholinesterase (AChE), thiobarbituric acid reactive substances (TBARS), protein carbonyl and catalase activity in tissues of piava (Leporinus obtusidens). LC(50)-96h was 5.0 mg L(-1) and the fish were exposed to 1/10 of LC(50)-96 h: 0.5 mg L(-1) of clomazone for 96 and 192h. The same parameters were also assayed after a recovery period of 192 h in clean water. AChE activity was reduced only in the brain and heart of fish exposed for 96 h. AChE activity was decreased in the brain, muscle and heart tissues after 192 h of exposure. After 192 h of recovery period, AChE activity remained diminished in brain and muscle and showed a decrease in eye. However, after 192 h of recovery, AChE activity in heart was recovered. Fish showed increased TBARS levels in brain at all experimental periods. TBARS levels decreased in liver and muscle tissues after 192 h of exposure. The increase in muscle TBARS persisted in fish transferred to clean water. Protein carbonyl in the liver was increased in all periods studied including the recovery period. Catalase activity was reduced during all periods. The present study demonstrates the occurrence of disorders in AChE, TBARS, protein carbonyl and catalase activity in piava. The results also show changes in fish after exposure to an environmentally relevant concentration of clomazone. Most effects observed persisted after the recovery period. Thus, these parameters may be used to monitor clomazone toxicity in fish.     

Seasonal variation of extracellular enzymatic activity (EEA) and its influence on metal speciation in a polluted salt marsh

The influence of salt marsh sediment extracellular enzymatic activity (EEA) on metal fractions and organic matter cycling was evaluated on a seasonal basis, in order to study the relation between organic matter cycles and the associated metal species. Metals in the rhizosediment of Halimione portulacoides were fractioned according to the Tessier's scheme and showed a similar pattern regarding the organic-bound fraction, being always high in Autumn, matching the season when organic matter presented higher values. Both organic-bound and residual fractions were always dominant, being the seasonal variations due to interchanges between these two fractions. Phenol oxidase and beta-N-acetylglucosaminidase had higher activities during the Spring and Summer, contrarily to peroxidase which had higher activity during Winter. Protease showed high activities in both Spring and Winter. These different periods of high organic matter hydrolysis caused two periods of organic metal bound decrease. Sulphatase peaks (Spring and Winter) matched the depletion of exchangeable metal forms, probably due to sulphides formation and consequent mobilization. This showed an interaction between several microbial activities affecting metal speciation.     

Processing and Properties of Mixtures of PHB-V with Post-consumer LDPE

Mixtures of poly-β-(hydroxybutyrate-co-valerate) PHB-V with virgin and post-consumer low density polyethylene (LDPE) were prepared by melt mixing in proportions of 100/0, 90/10, 80/20, 70/30 and 0/100 (wt/wt%). The mixtures were analysed by infrared spectroscopy, differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), melting flow index (MFI), tensile tests, scanning electron microscopy (SEM) and biodegradation in simulated soil. The DMTA and DSC curves of post-consumer LDPE suggested that this polymer was a mixture of LDPE and linear low density polyethylene (LLDPE). Virgin and post-consumer LDPE had lower MFI than PHB-V, but the blends showed higher index as the content of LDPE increased. The addition of LDPE reduced the tensile strength and Young’s modulus of the mixtures compared with PHB-V. SEM indicated poor interfacial adhesion between PHB-V and LDPE. PHB-V degraded slow and gradually, while both LDPE showed virtually no degradation under the conditions studied. The biodegradability of the blends depended on their composition and of the type of LDPE. LDPE improved the biodegradability of the mixtures.     

Mercury uptake and allocation in Juncus maritimus: implications for phytoremediation and restoration of a mercury contaminated salt marsh

Juncus maritimus is the most abundant macrophyte in Laranjo bay, a Portuguese salt marsh heavily polluted by mercury (Hg). With the aim to elucidate the role of this species in the salt marsh Hg cycling and restoration, plants were harvested between March 2006 and January 2008 from four locations differing in Hg contamination. Metal uptake and distribution between plant organs were evaluated, biomass and Hg pools were also determined. Results showed that J. maritimus may influence the sediment pH and Eh, thus increasing the Hg available for uptake. Most (95-98%) of the absorbed Hg was retained belowground, phytostabilizing the metal and reducing the amount of Hg in the sediments. These results suggest that in salt marshes dominated by J. maritimus the approach could be phytostabilization, where these plants can be used to immobilize metals and store them belowground, reducing the pool of bioavailable Hg within contaminated marshes and acting as a sink rather than a source of contamination to the surrounding areas.