Benthic foraminiferal response to trace element pollution—the case study of the Gulf of Milazzo, NE Sicily (Central Mediterranean Sea)

The response of benthic foraminiferal assemblages to trace element pollution in the marine sediments of the Gulf of Milazzo (north-eastern Sicily) was investigated. Since the 1960s, this coastal area has been a preferred site for the development of two small marinas and a commercial harbour as well as for heavy industry. Forty samples collected in the uppermost 3–4 cm of an undisturbed layer of sediment in the littoral environment were used for this benthic foraminiferal analysis. The enrichment factors (EFs) of selected trace elements (As, Co, Cr, Cu, Mn, Ni, Pb and Zn) were also calculated. Changes both in benthic foraminiferal assemblages and in some trace elements concentrations have provided evidence that the gulf’s littoral zone can be subdivided into three sectors characterised by environmental changes in the marine ecosystem. In the sector unpolluted, close to the Milazzo Cape, foraminiferal assemblages exhibit high values of species richness and foraminiferal density while trace element concentrations and their EFs are very low. Here, the highest densities of Miliolids and epiphytic species are present. On the contrary, in the sector polluted, from the marinas to the crude oil refinery, foraminiferal density and species diversity are low, and assemblages are dominated, albeit with very low densities, by species that tolerate stressed environmental conditions, such as LOFAs, agglutinants and Ammonia spp. Here, the highest trace elements concentrations of Pb, Zn and Cu and related EFs were detected. Eastwards, in the sector moderately polluted, foraminiferal populations are quite poor. They are characterised by low values of species richness and foraminiferal densities, nevertheless trace element concentrations become lower than in the other sectors and their EFs are often below 1. Deformed foraminifera, with percentages up to 7.14 %, were found in all three of the sectors. Differences in benthic foraminiferal assemblages, coupled with results from statistical analysis, indicate that anthropogenic trace element pollution could be considered as one of the most important causes of the modifications of foraminiferal assemblages in the study area.     

A Flexible Global Warming Index for Use in an Integrated Approach to Climate Change Assessment

Global Warming Potential (GWP) is an index used to measure the cumulative radiative forcing of a tonne of greenhouse house gas (GHG) relative to that of a ‘reference’ gas (CO₂). Under the Kyoto Protocol, GWP can be used as a fixed index to govern the trade-off between different GHGs in a multi-gas approach to GHGs abatement. The use of fixed GWPs has been criticized for not being very cost effective compared to the use of some flexible indices. To gain wider acceptance, however, a flexible index must also prove to be easy to use, and the economic gains from its adoption must be significant. In this paper, we develop a flexible index based on the concept of marginal rather than cumulative or average global warming potentials. These marginal global warming potentials (MGWPs) can be endogenously determined within a climate model given a particular climate objective based on radiative forcing level. The MGPWs are then linked to the marginal abatement costs of the GHGs, which are also endogenously determined within an economic model. When the two concepts are linked in this way, the result is a cost-effective way of achieving a particular climate change objective with multigas abatement. We show that the savings in costs when using this flexible MGPWs can be significant, and more importantly, they are not uniformly distributed across different regions.

Agent-based integrated assessment modelling: the example of climate change

Current approaches to deal with the socio-economic implications of climate change rely heavily on economic models that compare costs and benefits of different measures. We show that the theoretical foundations underpinning current approaches to economic modelling of climate change are inappropriate for the type of questions that are being asked. We argue therefore that another tradition of modelling, social simulation, is more appropriate in dealing with the complex environmental problems we face today.     

Methylmercury production in the water column of an ultraoligotrophic lake of Northern Patagonia, Argentina

Methyl-mercury (CH3Hg+) production was studied in freshwaters from lake Moreno, an ultraoligotrophic system belonging to Northern Patagonia. Hg2+ labelled with high specific activity 197Hg was spiked to water samples in concentrations of 10 ng l(-1), and incubated in laboratory for 3d time trends under different conditions. Experimental water was sampled daily to evaluate CH3(197)Hg+ production. Lake water used in the experiments was sampled just below the upper limit of the metalimnion ( approximately 30 m depth), where maximum values of chlorophyll a have been measured previously. Sampling was performed in late autumn, when the plankton fraction <50 microm exhibited mercury concentrations up to 260 microg g(-1) dry weight. The experiments analysed lake water filtered through 50, 20, and 0.2 microm (filter-sterilized) mesh nets. ASTM grade 1 water was also incubated for control. All the experiments were run in an environmental chamber under controlled temperature and light regime. High Hg2+ conversion to CH3Hg+, up to 50%, was measured in lake water, in a process stimulated by light. CH3Hg+ production was two-fold higher after 3d of incubation with illumination compared to total darkness. Sterile lake water showed conversions up to 30%, while the planktonic components seem to enhance the CH3Hg+ production. Overall, our results provide evidence that lake Moreno waters favour CH3Hg+ production in processes stimulated by light. Although biotic components certainly contribute to enhance mercury methylation, water chemistry plays a key role in this process. We hypothesize that dissolved organic matter, particularly its quality, could be decisive.     

Evolution of biodegradation of deinking by-products used as alternative cover material

Deinking by-products (DBP) have been used as alternative cover material for landfills and mine tailings. Since DBP is biodegradable because of its high cellulose and hemicellulose content, a laboratory experimental program was performed to monitor the evolution of biodegradation and changes in the physico-chemical and geotechnical properties of DBP samples submitted to accelerated biodegradation for 1460 days at 38 degrees C. The evolution of gas and leachate production was monitored in terms of both quality and quantity, which allowed for the calculation of mass loss with time. Under the conditions of the tests (no load applied), 19.6% of the mass was lost as gas, whereas 6.1% was leached out. The results show that biodegradation did not significantly alter the compaction behavior of DBP. The void ratio and water content increased significantly, while the volume of the samples slightly decreased. This seem to indicate that the porous structure of the samples was no longer the same after 1460 d of accelerated biodegradation. A slight increase in the relative density indicates that the organic/inorganic matter ratio increased. The results of permeability tests performed with samples at various stages of biodegradation and at various confining stresses show that the saturated hydraulic conductivity of recompacted biodegraded DBP decreased from 7 x 10(-7)cm/s to approximately 2 x 10(-7)cm/s, as biodegradation advanced.     

Anaerobic biodegradation of high strength 2-chlorophenol-containing synthetic wastewater in a fixed bed reactor

In this study the continuous treatment of 2-chlorophenol (2-CP) containing synthetic wastewater at increasing concentrations up to 2600 mg L-1 in an anaerobic fixed bed reactor was achieved. As a source of microorganisms municipal sewage sludge was acclimatised to maximally 50 mg L-1 2-CP by 3 successive feedings within 1.5 months. Then, an anaerobic fixed bed reactor was inoculated with this sludge and was operated for 318 d, during which the 2-CP influent concentration was stepwise increased from 50 to 2600 mg L-1 within 265 d. At a hydraulic retention time (HRT) of 2.2 d the 2-CP loading rate was 2 g L-1 d-1 and the average 2-CP removal rate was 0.87 g L-1 d-1, accounting for 73% removal. This is the highest 2-CP removal rate ever reported. The negative effect of a 2-CP loading rate of 1.36 g L-1 d-1 on 2-CP removal was reversible within 2 wk when lower loading conditions (e.g. 0.76 g 2-CP L-1 d-1) were re-established. The median chloride ion release per unit 2-CP degraded was 0.24, which was reasonably close to the theoretically expected value of 0.28. In a batch assay, carried out with relatively clear reactor effluent, the highest removal rate of 2-CP was 175 mg L-1 d-1. At the time of reactor termination on day 318, the 2-CP removal rate by the biofilm in the reactor was 0.61 g L-1 d-1, corresponding to a HRT of 3.4 d and a 2-CP loading rate of 0.76 g L-1 d-1. At these very stable conditions removal of COD was 84% and of 2-CP 81%     

Molecular size distribution of compost-derived humates as a function of concentration and different counterions

Conformational changes in the structures of humic acids (HA) extracted from compost with varying degrees of maturity were monitored by high performance size exclusion chromatography (HPSEC). The molecular size distribution of HA was compared in solutions containing sodium or ammonium counterions at pH 7 and pH 4.5. These findings indicate that the humates' molecular size depended not only on the nature of the counterions but also on their concentration in the solution. The physicochemical nature of sodium counterions determined smaller molecular sizes than those of the more hydrated ammonium counterions, at low concentrations of humates. Conversely, at higher humate concentrations, the more compact conformation of sodium humates produced larger molecular sizes than those of ammonium humates due to the aggregation of more hydrophobic surfaces in the sodium humates. Composting led to the degradation of labile microbial components with accumulation of hydrophobic constituents. This caused self-association of hydrophobic compounds into humic superstructures of larger molecular size over composting time. At lower pH, changes in conformational stability by the addition of acetic acid to humate solutions were explained by the supramolecular model of humified organic matter.     

Preliminary indications from atomic force microscopy of the presence of rapidly-formed nanoscale films on aquifer material surfaces

The objective of this study was to determine if there is a nanoscale surface film on aquifer-like materials exposed to deep groundwaters, as has previously been found on surfaces exposed to surface and soil waters. Such surface films will modify surface properties that are so important in determining the mobility of many groundwater pollutants. Muscovite mica was used because a) it is a good analogue for the main sorbing phases of many clastic aquifers and b) its cleavage planes are atomically flat allowing high resolution imaging. Freshly-cleaved muscovite plates were exposed to groundwater from a sandstone aquifer for 30 min, and surface properties (morphology, coverage, roughness and tip–substrate force interactions) were measured using atomic force microscopy (AFM). A patchy surface film of several nanometres in depth, incorporating larger separate particles, was found on the mica surface. This film was associated with significantly increased roughness values and AFM probe–sample interaction forces compared with pure water and inorganic (synthetic groundwater) solution controls. Although the results reported are preliminary in nature, if confirmed, such films are likely to affect sorption reactions, surface-facilitated redox interactions, non-aqueous phase liquid wetting angles, and colloid–pathogen–rock attachment, and will thus be of importance in understanding natural attenuation and migration of dissolved, non-aqueous and particulate phases in groundwaters.     

Volatile chlorinated hydrocarbons in Antarctic superficial snow sampled during Italian ITASE expeditions

In order to detect the presence of some volatile chlorinated hydrocarbons (VCHCs) and to understand their transport and deposition mechanism, superficial snow was sampled during two Italian ITASE (International Trans Antarctic Scientific Expedition) expeditions: the first traverse was carried out in 1998/1999 from Terra Nova Bay to Dome Concordia; the second traverse was carried out in 2001/2002 through Adélie, George V, Oates and Northern Victoria Lands. Some VCHCs (chloroform; 1,1,1-trichloroethane; tetrachloromethane; 1,1,2-trichloroethylene; tetrachloroethylene) were analysed using a highly sensitive and selective hyphenated technique composed of a purge-and-trap injector coupled to a gas chromatograph with a mass spectrometric detector (PTI-GC-MS) operating in SIM mode. Investigated VCHCs were present in all analysed snow samples with concentration levels of several units, tens, or sometimes hundreds of ng kg(-1). VCHC snow concentration levels remained approximately constant with changing distance from the coast and the comparison between fresh and aged snow did not show any substantial differences; on the basis of this evidence marine aerosol and dry deposition may be rejected as principal VCHC transport and deposition mechanism hypotheses. VCHC concentration levels in Antarctic snow samples were comparable to or greater than those found in snow from temperate zones.     

Validation of a passive atmospheric deposition sampler for polybrominated diphenyl ethers

An atmospheric deposition sampler was validated with respect to polybrominated diphenyl ethers (PBDEs), a compound group that is widely used as flame retardants in many types of consumer products. The deposition sampler consists of an adsorption cartridge that is connected to a glass funnel. Extraction tests with spiked cartridges using soxhlet extraction with acetone revealed recoveries of >80% for all of the investigated PBDEs. Once adsorbed, PBDEs are stable, as proven by extractions of spiked cartridges that were stored outdoors and collected after different periods of time, up to 84 days. High recoveries indicate that degradation of adsorbed PBDEs does not play a role under realistic field conditions. Bulk deposition rates of PBDEs were determined in a field test with 3 replicates, and a possible breakthrough of target compounds was assessed in the field using a second adsorption cartridge in series. No breakthrough of target compounds could be observed within a sampling period of 61 days, and a bulk deposition rate of approximately 1 ng m(-2) day(-1) for the sum of all analysed PBDEs was measured. The highest deposition rates were measured for octa-brominated congeners, followed by BDEs 99, 183, 153, and 47. Overall, the sampler was successfully validated regarding the atmospheric deposition of PBDEs.