Heavy metals extraction from contaminated soil: recovery of the flushing solution

The optimum conditions for the recovery of copper from a contaminated soil by using the soil flushing technique are evaluated. Tests on a soil artificially contaminated with copper chloride were carried out in order to evaluate the influence of the speed of percolation and of the chelating agent concentration (aqueous solution of an ethylendiaminotetraacetic acid di-sodium salt Na2-EDTA). At pH=7.3 an efficiency up to 93.9% for copper extraction was achieved by flushing 500 ml of Na2-EDTA 0.05 M solution and 100 ml of pure water at 0.792 cm/h. At these operating conditions the formation of EDTA complexes with other competitive cations (calcium and iron) was negligible. The experimental results were in agreement with the ones obtained using a model describing the chemistry of metal extraction. This model assessed that above pH=6 the formation of calcium and iron EDTA complexes was excluded and only the chelation of copper was allowed. The recovery of 91.6% of EDTA was also achieved by evaporating and acidifying the extracted solution: after filtration, solid EDTA was obtained, through the addition of sodium hydroxide Na2-EDTA. About 99.5% of the extracted copper was finally precipitated under alkaline conditions from the liquid phase.     

Imposex as a biomonitoring tool for marine pollution by tributyltin: some further observations

Imposex, i.e., the imposition of male sexual characteristics on female neograstropods, has been used worldwide as a bioindicator of pollution by the antifouling agent TBT as well as to assess the related ecological impact. The recent total ban on the use of TBT in the maritime industry has been partly based on the use of such a biomarker. This is mainly based on the assumption that no other pollutant, or environmental stress, is able to induce such a biological response. Nonetheless, several authors had challenged this idea. The present paper will present further field observations on imposex in Hexaplex trunculus from Malta (Central Mediterranean) which may help clarify this issue. Furthermore, the incidence of imposex in this species will be related to body burdens and to the environmental levels of organotins as measured analytically. First histological observations will also be presented which may help clarify the ecological significance of this response in this species. Finally a number of alternative scenarios regarding the relationship between imposex and TBT will be discussed.     

Water farms and transfer conflicts in Arizona,USA: A proposed resolution process

Water is a relatively scarce resource in Arizona, especially since the recent urban growth booms of Phoenix and Tucson. Arizona's 1980 Groundwater Management Act was the precursor to current water-transfer conflicts between urban buyers, rural farmers, and third parties. Water farms are bought with the intention to transfer their appurtenant groundwater to the two major metropolitan areas. As water markets have emerged, differing values and public interest issues have become apparent, while the state legislature attempts to resolve inequities. Site-specific transfer disputes, as well as policy-making conflicts, offer suitable situations for a mediation process. Equity- and efficiency-based criteria are suggested as the basis for resolving water-transfer conflicts, and a mediation process is proposed. However, third parties must develop an agenda, and a balance of power should be attained before mediation can effectively forge an agreement on water-transfer policies. The attainment of statewide policies generated through a mediated process has the potential to expand long-range regional water planning and management.     

Monitoring the quality of the marine environment

As part of the monitoring program from Instituto Hidrográfico, since 1981 sediment and water samples have been collected from four different estuarine areas located along the continental coast of Portugal. The concentrations of different parameters were measured in the water and sediment samples. After normalization, the concentrations of chromium, mercury, lead and zinc in the sediments from the different areas were compared.     

Relationships between psychological climate perceptions and work outcomes: a meta‐analytic review

In this study, meta‐analytic procedures were used to examine the relationships between individual‐level (psychological) climate perceptions and work outcomes such as employee attitudes, psychological well‐being, motivation, and performance. Our review of the literature generated 121 independent samples in which climate perceptions were measured and analyzed at the individual level. These studies document considerable confusion regarding the constructs of psychological climate, organizational climate, and organizational culture and reveal a need for researchers to use terminology that is consistent with their level of measurement, theory, and analysis. Our meta‐analytic findings indicate that psychological climate, operationalized as individuals' perceptions of their work environment, does have significant relationships with individuals' work attitudes, motivation, and performance. Structural equation modeling analyses of the meta‐analytic correlation matrix indicated that the relationships of psychological climate with employee motivation and performance are fully mediated by employees' work attitudes. We also found that the James and James ( 1989 ) PC_g model could be extended to predict the impact of work environment perceptions on employee attitudes, motivation, and performance. Despite the number of published individual‐level climate studies that we found, there is a need for more research using standardized measures so as to enable analyses of the organizational and contextual factors that might moderate the effects of psychological climate perceptions. Finally, we argue for a molar theory of psychological climate that is rooted in the psychological processes by which individuals make meaning or their work experiences. Copyright © 2003 John Wiley & Sons, Ltd.     

Prediction of contaminant transport in fractured carbonate aquifer types: a case study of the Permian Magnesian Limestone Group (NE England,UK)

Viruses and bacteria which are characterized by finite lives in the subsurface are rapidly transported via fractures and cavities in fractured and karst aquifers. Here, we demonstrate how the coupling of a robust outcrop characterization and hydrogeophysical borehole testing is essential for prediction of contaminant velocities and hence wellhead protection areas. To show this, we use the dolostones of the Permian Magnesian Limestone aquifer in NE England, where we incorporated such information in a groundwater flow and particle tracking model. Within this aquifer, flow in relatively narrow (mechanical aperture of ~?10^?1–1 mm) fractures is coupled with that in pipe cavities (~?0.20-m diameter) following normal faults. Karstic cavities and narrow fractures are hydraulically very different. Thus, the solutional features are represented within the model by a pipe network (which accounts for turbulence) embedded within an equivalent porous medium representing Darcian flowing fractures. Incorporation of fault conduits in a groundwater model shows that they strongly influence particle tracking results. Despite this, away from faulted areas, the effective flow porosity of the equivalent porous medium remains a crucial parameter. Here, we recommend as most appropriate a relatively low value of effective porosity (of 2.8?×?10^?4) based on borehole hydrogeophysical testing. This contrasts with earlier studies using particle tracking analyses on analogous carbonate aquifers, which used much higher values of effective porosity, typically ~?10² times higher than our value, resulting in highly non-conservative estimates of aquifer vulnerability. Low values of effective flow porosities yield modelled flow velocities ranging from ~?100 up to ~?500 m/day in un-faulted areas. However, the high fracturing density and presence of karstic cavities yield modelled flow velocities up to ~?9000 m/day in fault zones. The combination of such flow velocities along particle traces results in 400-day particle traces up to 8-km length, implying the need for large well protection areas and high aquifer vulnerability to slowly degrading contaminants.

     

Climate change and disaster management

Climate change, although a natural phenomenon, is accelerated by human activities. Disaster policy response to climate change is dependent on a number of factors, such as readiness to accept the reality of climate change, institutions and capacity, as well as willingness to embed climate change risk assessment and management in development strategies. These conditions do not yet exist universally. A focus that neglects to enhance capacity-building and resilience as a prerequisite for managing climate change risks will, in all likelihood, do little to reduce vulnerability to those risks. Reducing vulnerability is a key aspect of reducing climate change risk. To do so requires a new approach to climate change risk and a change in institutional structures and relationships. A focus on development that neglects to enhance governance and resilience as a prerequisite for managing climate change risks will, in all likelihood, do little to reduce vulnerability to those risks.     

Evaluation of chemical and ecotoxicological characteristics of biodegradable organic residues for application to agricultural land

The use of organic waste and compost as a source of organic matter and nutrients is a common practice to improve soil physico-chemical properties, meanwhile reducing the need for inorganic fertilisers. Official guidelines to assess sewage sludge and compost quality are mostly based on total metal content of these residues. Measurement of the total concentration of metals may be useful as a general index of contamination, but provides inadequate or little information about their bioavailability, mobility or toxicity when the organic residue is applied to the soil. However, ecotoxicity tests provide an integrated measure of bioavailability and detrimental effects of contaminants in the ecosystem. In the present study, three different types of biodegradable organic residues (BORs) have been considered: sewage sludge from municipal wastewater treatment (SS), compost from the organic fraction of unsorted municipal solid waste (MSWC), and garden waste compost (GWC). The BORs were subjected to chemical characterisation and total metal quantification (Cd, Cr, Cu, Ni, Pb and Zn), in order to verify their suitability for land application. Water leachability was determined through the DIN 38414-S4 method, while the modified BCR sequential extraction procedure was used for metal speciation. Ecotoxicity of the BORs was studied by direct and indirect bioassays. Direct toxicity bioassays were: plant growth tests with cress (Lepidium sativum L.) and barley (Hordeum vulgare L.), and earthworm (Eisenia fetida) mortality. On the other hand, indirect exposure bioassays, with leachate from the residues, took into account: luminescent bacteria (Vibrio fischeri), seed germination (L. sativum and H. vulgare) and Daphnia magna immobilization. As far as total metal concentration is concerned, with particular reference to Zn, SS resulted neither suitable for the use in agriculture nor compatible to be disposed of as an inert material into landfill, according to the Directive 1999/31/EC. Zinc in SS was mainly present in exchangeable form (28.5%), appearing as highly bioavailable. As a consequence, SS exhibited either high ecotoxicity effects with the indirect exposure bioassays or significant mortality with the earthworm bioassay. Total content of metals in MSWC allowed its classification as "stabilised biowaste", according to 2nd draft [DG Env.A.2. Working document of Biological treatment of biowaste - 2nd draft. Directorate-General Environment, Brussels, 12th February; 2001. accessed in:http://europa.eu.int/comm/environment/waste/facts_en.htm, at 10/09/2002] while leachate, on the basis of the concentration of these contaminants, could be classified as "inert waste". This residue showed significant ecotoxicity effects with direct exposure bioassays as well as with the luminescent bacteria bioassay. However, it resulted less toxic than SS. Finally, GWC could be classified as a Class 2 compost, with no detectable toxic effects on the organisms used in the bioassays, except for the luminescent bacteria. In this case, an EC(50) of 73.0% was observed. Considering the results, the use of a battery of toxicity test in conjunction with chemical analysis should be suggested, in order to correctly assess possible environmental risks deriving from disposal or land application of biodegradable organic residues.     

Effect of liquid cow manure on andisol properties and atrazine adsorption

Application of animal manure amendments to agricultural soils is a common practice to improve soil fertility through the addition of essential plant nutrients. This practice may increase the potential for atrazine (2-chloro-4-ethylamino-6-isopropylamino-1, 3, 5-triazine) leaching due to competition for adsorption sites between the pesticide and dissolved organic carbon (DOC) added through manure. We evaluated the influence of liquid cow manure (LCM) application on soil properties, atrazine adsorption, and the physicochemical controlling mechanisms in an Andisol. The LCM was applied at rates equivalent to 0, 100,000, 200,000, and 300,000 L ha(-1), resulting in treatments S-0, S-100, S-200, and S-300, respectively. The LCM application increased DOC and pH of the soils immediately on addition, but pH returned to S-0 values 30 d after application. The LCM application did not modify atrazine adsorption with the two lowest application rates (S-100 and S-200), but atrazine adsorption was decreased in S-300 (K(f) = 0.96) compared with the control (S-0) (K(f) = 1.19), possibly due to the competitive adsorption of DOC with the pesticide. The Fourier-transformed infrared analysis showed that LCM increased aliphaticity and presence of N-containing groups and polysaccharide-like groups in amended soils; however, these properties did not modify the atrazine interaction in the studied amended soils. Interestingly the addition of DOC to soil at the high application rate (S-300) reduced atrazine adsorption in this rich OM Andisol despite the LCM not raising the concentration of stable organic matter. The application of high rates of liquid manure containing DOC incurs an increased risk of pesticide leaching.     

Polychlorinated biphenyls in contaminated soil samples evaluated by GC-ECD with dual-column and GC-HRMS

We present and compare results obtained from the analysis of polychlorinated biphenyls (PCBs) of a limited number of contaminated soil samples collected in three areas of Basilicata region (south of Italy). The levels of PCBs were evaluated by using two analytical methods: (i) parallel dual-column gas-chromatography with dual electron capture detectors (GC-ECD) and (ii) gas-chromatography coupled to high-resolution mass spectrometry (GC-HRMS) via electron impact ionization (EI) in the multiple ion monitoring mode (MIM, two ions per compound). Two extraction methods prior to sample cleanup were also examined: microwave-assisted extraction (MAE) and ultrasonic-assisted extraction (UAE). The MAE was the extraction procedure adopted using acetone/n-hexane (1:1, v/v) as it is mainly characterized by higher sample throughput and allowed reduced consumption of organic solvents. While extraction and analysis of spiked soil samples showed the applicability of both methods, systematic differences between the results were obtained for the sum of PCBs as a result of some non-detected congeners by GC-ECD compared with GC-HRMS. Indeed, high resolution MS using EI mode (electron energy 40eV) with a resolving power of 10,000 provides additional information about the contamination pattern. The GC-ECD screening of 11 soil samples led to just one sample non-compliant to as it was close to the guide value for soils fixed by the Italian legislation (i.e., 60ppb for private or urban soil). Using GC-HRMS, the amount of all PCBs found ranged from 5.4 to 127ppb with five soil samples non-compliant to the guide value. The number of identified congeners ranged from 1 to 9 and 9 to 18 using dual-column GC-ECD and GC-HRMS, respectively.