Column experiments to assess the effects of electron donors on the efficiency of in situ precipitation of Zn,Cd, Co and Ni in contaminated groundwater applying the biological sulfate removal technology

BACKGROUND, AIMS AND SCOPE: In a previous study, we explored the use of acetate, lactate, molasses, Hydrogen Release Compound (HRC, which is based on a biodegradable poly-lactate ester), methanol and ethanol as carbon source and electron donor to promote bacterial sulfate reduction in batch experiments, this with regards to applying an in situ metal precipitation (ISMP) process as a remediation tool to treat heavy metal contaminated groundwater at the site of a nonferrous metal work company. Based on the results of these batch tests, column experiments were conducted with lactate, molasses and HRCI as the next step in our preliminary study for a go-no go decision for dimensioning an on site application of the ISMP process that applies the activity of the endogenous population of sulfate-reducing bacteria (SRB). Special attention was given to the sustainability of the metal precipitation process under circumstances of changing chemical oxygen demand (COD) to [SO4(2-)] ratios or disrupted substrate supply. METHODS: To optimize the ISMP process, an insight is needed in the composition and activity of the indigenous SRB community, as well as information on the way its composition and activity are affected by process conditions such as the added type of C-source/ electron donor, or the presence of other prokaryotes (e.g. fermenting bacteria, methane producing Archaea, acetogens). Therefore, the biological sulfate reduction process in the column experiments was evaluated by combining classical analytical methods [measuring heavy metal concentration, SO4(2-)-concentration, pH, dissolved organic carbon (DOC)] with molecular methods [denaturing gradient gel electrophoresis (DGGE) fingerprinting and phylogenetic sequence analysis] based on either the 16S rRNA-gene or the dsr (dissimilatory sulfite reductase) gene, the latter being a specific biomarker for SRB. RESULTS AND DISCUSSION: All carbon sources tested promoted SRB activity, which resulted within 8 weeks in a drastic reduction of the sulfate and heavy metal contents in the column effluents. However, unexpected temporal decreases in the efficiency of the ISMP process, accompanied by the release of precipitated metals, were observed for most conditions tested. The most dramatic observation of the failing ISMP process was observed within 12 weeks for the molasses amended column. Subsequent lowering the COD/ SO4(2-) ratio from 1.9 to 0.4 did not alter the outcome of sulfate reduction and metal precipitation efficiency in this set-up. Remarkably, after 6 months of inactivity, bacterial sulfate reduction was recovered in the molasses set up when the original COD/ SO4(2-) ratio of 1.9 was applied again. Intentional disruption of the lactate and HRC supplies resulted in an immediate stagnation of the ISMP processes and in a rapid release of precipitated metals into the column effluents. However, the ISMP process could be restored after substrate amendment. 16S rDNA-based DGGE analysis revealed that the SRB population, in accordance with the results of the previously performed batch experiments, consisted exclusively of members of the genus Desulfosporosinus. The community of Archaea was characterized by sequencing amplicons of archaeal and methanogen-specific PCR reactions. This approach only revealed the presence of non-thermophilic Crenarchaeota, a novel group of organisms which is only distantly related to methane producing Euryarchaeota. DGGE on the dsrB genes was successfully used to link the results of the ISMP process to the community composition of the sulfate reducing bacteria. CONCLUSIONS: In the case of an intentional disruption of substrate supply, the ISMP process failed most likely because the growth and activity of the indigenous SRB community stopped due to a lack of a carbon and electron donor. On the other hand, the cause of the sudden temporal shortcomings of the ISMP process in the presence of different substrates was not immediately clear. It was first thought to be the result of competition between methanogenic prokaryotes (MP) and sulfate reducers, since the formation of small amounts of CH4 (0.01-0.03 ppm ml(-1) was detected. However, the results of molecular analyzes indicate that methanogens do not constitute a major fraction of the microbial communities that were enriched in the column experiments. Therefore, we postulate that the SRB population becomes inhibited by the formed metal sulfides. RECOMMENDATION AND PERSPECTIVE: Our results indicate that the ISMP process is highly dependent on SRB-stimulation by substrate amendments and suggest that this remedial approach might not be viable for long-term application unless substrate amendments are continued and environmental conditions are strictly controlled. This will include the removal of affected aquifer material from the metal precipitation zone at the end of the remediation process, or removal of metal precipitates when the microbial activity decreases. Additional tests are necessary to investigate what will happen when clear groundwater passes through the reactive zone while no more C-sources are amended and all indigenous carbon is consumed. Also, the effects of dramatic increases in sulfate- or HM-concentrations on the SRB-community and the concomitant ISMP process need to be studied in more detail.     

Range-wide Yangtze freshwater dolphin expedition: The last chance to see Baiji?

BACKGROUND, AIM AND SCOPE: There are two species of fresh water cetaceans surviving in the Yangtze River system in China: Baiji (Lipotes vexillifer) and Yangtze finless porpoise (Neophocaena phocaenoides asiaeorientalis). As a result of the expansion of human activities on the river, their distribution ranges appear to be decreasing and in the case of the Baiji, are even being restricted to several sections. The Baiji is the world's most critically endangered cetacean species with a population estimated at only a few tens of individuals. The Yangtze finless porpoise is the world's only freshwater-adapted population of the species, and it has been estimated that only around 1,000 individuals remain in the river system. In order to prevent the extinction of Baiji and a sharp decline in the abundance of the porpoise, in situ conservation (i.e. in the river) and two ex situ conservation (i.e. in semi-natural reserves and in captivity) strategies were proposed and have been implemented since the early 1990s. In view of both the severely endangered status of the animals and the severely degraded conditions of their habitats, the feasibility and actual status of these two strategies are raised for discussion. MAIN FEATURES: The threats faced by the cetaceans are mainly from the unfettered exploitation of the river's resources. In the past 20 years, five nature reserves have been established along the river. Imposing maximum prohibition of harmful and illegal fishing methods in the reserves might prolong the process of extinction of these cetaceans in the wild, but so far, the administrative measures taken in the reserves have not yet kept the abundance from sharply declining. As human use of the river and its resources is expected to intensify for many decades into the future, the ability of the river to continue to support these species is certainly undecided. Therefore, rescuing animals from the river and establishing viable breeding populations in seminatural reserves, in which the environment is similar to the main stream of the river, and in captivity, has to be considered urgently as the short-term goal of ex situ strategies. Since the abundance of porpoises is higher than that of the Baiji, we have first established breeding populations of them in the semi-natural reserves and in captivity. But, considering the extremely low density of Baiji in the river, an immediate range-wide Yangtze Baiji survey is an urgent need for locating and capturing sufficient Baiji for successfully establishing a breeding population of them in semi-natural reserves. RESULTS: Two semi-natural reserves (in Shishou, Hubei Province, and Tongling, Anhui Province) have been set up along the river in order to establish breeding populations of the Baiji and the porpoises. So far, several small groups of porpoises that were caught in the main stream of the river have successively been introduced into the semi-natural reserves. Under careful management, these animals in both of the semi-natural reserves not only survive, but can also reproduce naturally and successfully. At least one or three calves were born in each reserve each year. Additionally, a breeding group of porpoises is being established at the Baiji Dolphinarium at the Institute of Hydrobiology, Chinese Academy of Sciences, Wuhan. There are presently four adults and one calf living in the Dolphinarium. The calf, born in July, 2005, is the first captive bred Yangtze Finless Porpoise in the world. In preparation for the range-wide Yangtze cetacean survey, a 9-day pilot expedition on the river near Wuhan was conducted in March, 2006, in order to develop methods for locating the Baiji. No Baiji were expected to be seen in such a short period but about 40 porpoise sightings were observed. Results of the pilot survey indicated that traditional visual and acoustical survey methods for cetaceans should be adapted to find the elusive Baiji in the river. Currently, the range-wide Yangtze cetacean survey is in preparation. The survey will cover over 1,700 km of the Yangtze River from Yichang to Shanghai, and is expected to provide detailed information on Baiji and porpoise numbers and distribution patterns in the river. DISCUSSION: Although the short-term goal of ex situ conservation is to rescue cetaceans from the river and to establish viable breeding populations in semi-natural reserves and in captivity, the long-term goal of releasing the animals back into the river when the threats have decreased and the natural environment has been improved, should not be neglected. Moreover, the in situ conservation efforts in the natural reserves, and even in the entire Yangtze River system, including the lakes, should not be ignored or abandoned at any time. The activities contributing to the conservation of the Baiji and the porpoise in the wild have the incidental effect of benefiting the entire Yangtze ecosystem and other rare threatened species. The dynamics of the groups of porpoises in semi-natural reserves should be monitored continually, in order to guide the establishment of breeding groups of Baiji in these semi-natural reserves in the near future. CONCLUSIONS: Under the existing severely degraded conditions of the Yangtze system, the sharply fall populations of Baiji and porpoises will not be suspended in the foreseeable future. Therefore, ex situ conservation should be emphasized, and the severely threatened Baiji in the river should be removed and translocated to semi-natural reserves for establishing viable breeding populations. The successful program of capturing, translocating and maintaining finless porpoises in the Shishou semi-natural reserve has demonstrated its adequacy as an ex situ environment for cetaceans. Following the successful pilot survey in the river, the immediate range-wide Yangtze cetacean survey is proposed and is in preparation. The range-wide survey is expected to ensure that any remaining Baiji can be found reliably and captured successfully after the survey. RECOMMENDATIONS AND PERSPECTIVES: During the range-wide survey, not only the Baiji but also the porpoise as well as their habitats should be investigated based on visual and acoustical methods that adapted to the river and the animals. Meanwhile, the current risk levels to the Baiji and porpoises should be evaluated at each area where Baiji or porpoises can be reliably sighted. Any capture efforts should be targeted on the most threatened areas, or where there is maximum risk of injury or death. The immediate track of the Baiji should be carried out once a Baiji is sighted during the range-wide survey in order to obtain the movement route of the animals, which is crucial information for the successful capture operation. Additionally, the need to establish new semi-natural reserves for the porpoises should be placed on the agenda of local and central governments in the near future.     

Chemical Partitioning to Foliage: The Contribution and Legacy of Davide Calamari

- DOI: http://dx.doi.org/10.1065/espr2006.01.002 Background Davide Calamari and his colleagues were among the first to appreciate that vegetation could play a key role in determining the fate and effects of organic contaminants. They conducted pioneering experiments to investigate the uptake of contaminants by plants from the atmosphere and they sought to model the observed phenomena. In the nearly two decades since there has been a marked increase in understanding of these phenomena as a result of both experimental and modelling studies. - Goal. In this study we briefly review our current understanding of chemical partitioning between foliage and air. A model in both fugacity and concentration format is described, based on that of Tolls and McLachlan (1994), in which the leaf is treated as consisting of two layers, a waxy cuticle with an underlying 'reservoir' layer, the cuticle being surrounded by an air boundary layer and containing stomata that provide direct access from the air to the 'reservoir'. The model quantifies the dynamic penetration of a defined chemical into a defined leaf as a function of time. Main Features The model is applied for illustrative purposes to a hypothetical but typical leaf for a set of illustrative chemicals to demonstrate the effect of changes in physical-chemical properties and leaf characteristics. Discussion The results are compared qualitatively with a variety of field and laboratory studies of foliage uptake and clearance of chemicals. Conclusion It is concluded that the model yields results that are generally consistent with observations. It is suggested that with appropriate parameterisation and validation, the model can contribute to an improved understanding of the process of foliage uptake from the atmosphere and to the development of an improved predictive capability.     

Idle emissions from heavy-duty diesel vehicles: review and recent data

Heavy-duty diesel vehicle idling consumes fuel and reduces atmospheric quality, but its restriction cannot simply be proscribed, because cab heat or air-conditioning provides essential driver comfort. A comprehensive tailpipe emissions database to describe idling impacts is not yet available. This paper presents a substantial data set that incorporates results from the West Virginia University transient engine test cell, the E-55/59 Study and the Gasoline/Diesel PM Split Study. It covered 75 heavy-duty diesel engines and trucks, which were divided into two groups: vehicles with mechanical fuel injection (MFI) and vehicles with electronic fuel injection (EFI). Idle emissions of CO, hydrocarbon (HC), oxides of nitrogen (NOx), particulate matter (PM), and carbon dioxide (CO2) have been reported. Idle CO2 emissions allowed the projection of fuel consumption during idling. Test-to-test variations were observed for repeat idle tests on the same vehicle because of measurement variation, accessory loads, and ambient conditions. Vehicles fitted with EFI, on average, emitted approximately 20 g/hr of CO, 6 g/hr of HC, 86 g/hr of NOx, 1 g/hr of PM, and 4636 g/hr of CO2 during idle. MFI equipped vehicles emitted approximately 35 g/hr of CO, 23 g/hr of HC, 48 g/hr of NOx, 4 g/hr of PM, and 4484 g/hr of CO2, on average, during idle. Vehicles with EFI emitted less idle CO, HC, and PM, which could be attributed to the efficient combustion and superior fuel atomization in EFI systems. Idle NOx, however, increased with EFI, which corresponds with the advancing of timing to improve idle combustion. Fuel injection management did not have any effect on CO2 and, hence, fuel consumption. Use of air conditioning without increasing engine speed increased idle CO2, NOx, PM, HC, and fuel consumption by 25% on average. When the engine speed was elevated from 600 to 1100 revolutions per minute, CO2 and NOx emissions and fuel consumption increased by >150%, whereas PM and HC emissions increased by approximately 100% and 70%, respectively. Six Detroit Diesel Corp. (DDC) Series 60 engines in engine test cell were found to emit less CO, NOx, and PM emissions and consumed fuel at only 75% of the level found in the chassis dynamometer data. This is because fan and compressor loads were absent in the engine test cell.     

Absorbed dose in target cell nuclei and dose conversion coefficient of radon progeny in the human lung

To calculate the absorbed dose in the human lung due to inhaled radon progeny, ICRP focussed on the layers containing the target cells, i.e., the basal and secretory cells. Such an approach did not consider details of the sensitive cells in the layers. The present work uses the microdosimetric approach and determines the absorbed alpha-particle energy in non-spherical nuclei of target cells (basal and secretory cells). The absorbed energy for alpha particles emitted by radon progeny in the human respiratory tract was calculated in basal- and secretory-cell nuclei, assuming conical and ellipsoidal forms for these cells. Distributions of specific energy for different combinations of alpha-particle sources, energies and targets are calculated and shown. The dose conversion coefficient for radon progeny is reduced for about 2mSv/WLM when conical and ellipsoidal cell nuclei are considered instead of the layers. While changes in the geometry of secretory-cell nuclei do not have significant effects on their absorbed dose, changes from spherical to conical basal-cell nuclei have significantly reduced their absorbed dose from approximately 4 to approximately 3mGy/WLM. This is expected because basal cells are situated close to the end of the range of 6MeV alpha particles. This also underlines the significance of better and more precise information on targets in the T-B tree. A further change in the dose conversion coefficient can be achieved if a different weighting scheme is adopted for the doses for the cells. The results demonstrate the necessity for better information on the target cells for more accurate dosimetry for radon progeny.     

Low frequency electromagnetic waves as a supplemental energy source to sustain microbial growth?

Microbial populations in tetra-distilled water collapsed when cultured in a permalloy chamber shielding the populations from the suns and earths electromagnetic field, but thrived when cultured in an ordinary thermostat open to the electromagnetic field. Theoretically, protons in liquid water can be excited at their natural resonance frequencies through Langmuir oscillations and obtain enough kinetic energy to charge the transmembrane potential of a cell. Microbes may be capable of converting this energy into chemical energy to supplement their energy needs.     

Toxicity and heavy metal contamination of surficial sediments from the Bay of Thessaloniki (Northwestern Aegean Sea) Greece

Surficial sediments (the fraction < 2000 microm) from the Bay of Thessaloniki, in the Northwestern Aegean Sea, Greece were examined for heavy metal and organic carbon contents, as well as for acute LUMIStox toxicity of pore waters (PWs), wet sediment elutriates (WSEs) and dry sediment elutriates (DSEs) obtained from the solid material remaining after PW extraction. WSEs where not toxic. EC20/50 values could be measured in some DSE and PW samples. In all sediment samples, the DSE toxicity was greater than the corresponding PW toxicity. Sediment concentrations of total and labile Cd, Pb, Cu, Cr, Zn, Mn, Ni and Fe were determined and evaluated in relation to sediment quality guidelines. Pollution levels ranged from low to high for certain metals. A misfit between sediment toxicities calculated from heavy metal concentrations and those biologically measured was observed. Toxicity values were in general poorly correlated with sediment's heavy metal or organic carbon content. As significant correlation was however found between the DSE toxicity with total Ni and labile Fe, as well as for the PW toxicity with total Ni, labile Fe and labile Cr.     

Spider, bee, and bird communities in cities are shaped by environmental control and high stochasticity

Spatially organized distribution patterns of species and communities are shaped by both autogenic processes (neutral mechanism theory) and exogenous processes (niche theory). In the latter, environmental variables that are themselves spatially organized induce spatial structure in the response variables. The relative importance of these processes has not yet been investigated in urban habitats. We compared the variance explained by purely spatial, spatially structured environmental, and purely environmental components for the community composition of spiders (Araneae), bees (Apidae), and birds (Aves) at 96 locations in three Swiss cities. Environmental variables (topography, climate, land cover, urban green management) were measured on four different radii around sampling points (< 10 m, 50 m, 250 m, 1000 m), while Moran's eigenvector maps (MEMs) acted as spatial variables. All three taxonomic groups showed weak spatial structure. Spider communities reacted to very fine-scaled environmental changes of lawn and meadow management and climate. Bird community composition was determined by woody plants as well as solar radiation at all radii, the scale of the influence varying among species. Bee communities were weakly explained by isolated variables only. Our results suggest that the anthropogenic structuring of urban areas has disrupted the spatial organization of environmental variables and inhibited the development of biotic spatial processes. The near absence of spatial structure may therefore be a feature typical of urban species assemblages, resulting in urban community composition mainly influenced by local environmental variables. Urban environments represent a close-knit mosaic of habitats that are regularly disturbed. Species communities in urban areas are far from equilibrium. Our analysis also suggests that urban communities need to be considered as being in constant change to adapt to disturbances and changes imposed by human activities.     

Extraction of heavy metal ions from waste colored glass through phase separation

A new method utilizing phase separation phenomena for the extraction of heavy metal ions used as colorants in colored glass is proposed. Colored soda-lime-silica glass containing Co or Cr as a colorant was remelted with B2O3 to yield soda-lime-borosilicate glass. The soda-lime-borosilicate glass thus obtained was leached in 1M nitric acid at 90 degrees C to dissolve the borate phase. All cations (Na, Ca, Cr and Co) concentrated in the borate phase are successfully leached out with the dissolution of the borate phase, when the amount of the B2O3 added to the glass and heat treatment conditions are properly chosen. Porous silicate glass powders with high SiO2 purity are obtained as the result of the leaching. Porous glass can also be formed as bulk material by controlling the composition of additives during the remelting.