Benzene oxidation under sulfate-reducing conditions in columns simulating in situ conditions.

The oxidation of benzene under sulfate-reducing conditions was examined in column and batch experiments under close to in situ conditions. Mass balances and degradation rates for benzene oxidation were determined in four sand and four lava granules filled columns percolated with groundwater from an anoxic benzene-contaminated aquifer. The stoichiometry of oxidized benzene, produced hydrogen carbonate and reduced sulfate correlated well with the theoretical equation for mineralization of benzene with sulfate as electron acceptor. Mean retention times of water in four columns were determined using radon ((222)Rn) as tracer. The retention times were used to calculate average benzene oxidation rates of 8-36 microM benzene day(-1). Benzene-degrading, sulfide-producing microcosms were successfully established from sand material of all sand filled columns, strongly indicating that the columns were colonized by anoxic benzene-degrading microorganisms. In general, these data indicate a high potential for Natural Attenuation of benzene under sulfate-reducing conditions at the field site Zeitz. In spite of this existing potential to degrade benzene with sulfate as electron acceptor, the benzene plume at the field site is much longer than expected if benzene would be degraded at the rates observed in the column experiment, indicating that benzene oxidation under sulfate-reducing conditions is limited in situ.

Records of polychlorinated biphenyls (PCBs) in sediments of four remote Chilean Andean Lakes.

Sediment cores from four Chilean lakes along the Andes Chain (Chungará, Laja, Castor and Venus) were analysed in order to investigate PCB concentrations and distributions in sediment samples. Sediment cores were analysed for PCBs using gas chromatography (GC-ECD/MS) and radioisotopically dated using 210Pb. Organic carbon content (OC) and 210Pb fluxes were also measured. Results showed that sediment PCB concentrations (ngg(-1) d.w.) at Lake Chungará (1.2 +/- 1) in northern Chile, Laja (5 +/- 4) in central, and in Lake Castor (3.5 +/- 4) in southern Chile (the eastern side of the Andes Mountain) were lower than sediments collected from Lake Venus (64 +/- 30) located in southern Chile (the western side) which contained 15-fold higher concentrations of PCBs. The percentage (%) of organic carbon was variable and showed a high range of values in the sediment fluctuating from 2% (Lake Laja) to 22% (Lake Chungará). Analysis of 210Pb fluxes, presented a decrease trend following Lake Laja>Castor>Chungará with a positive correlation with rainfall at each site. Sedimentation rates in Lake Castor (1846 gm(-2)yr(-1)) were higher than at Chungará (748 gm(-2)yr(-1)) and Lake Laja (508 gm(-2)yr(-1)). Focusing factor (FF) is used as a tool to elucidate PCB input in the aquatic ecosystem. FF were lower (<1) for the shallower lakes (Lakes Chungará and Castor). This study provides background levels of PCBs at remote lakes in Chile. Differences in geographical characteristics (orographic effect) might play an important role in the arrival of PCBs, particularly into the southern lakes. PCB fluxes indicated deposition of PCBs in recent sediments is higher than in previous years with peaks of PCB between 1991 and 1998. The continuing increase of PCB inputs in remote Chilean lakes, could be associated with long range atmospheric transport (LRAT).

Flooding of lignite mines: isotope variations and processes in a system influenced by saline groundwater.

The quality of both groundwaters and surface waters that arise during flooding of abandoned lignite open pits are influenced by regional and local factors. A typical regional factor is due to oxidised sedimentary sulfides. A more local factor is the interaction of shallow water with highly saline groundwater, which is important in Merseburg-Ost (Germany). Investigation of this system is aided by the use of many environmental isotope tracers but special problems can arise. In order to reveal processes in the mine environment (shallow groundwater, lake water) and to characterise mixtures with saline groundwater results are described using the tracers deltaD, delta18O, delta13C, delta34S, 87Sr/86Sr, 3H, 14C, 39Ar, and 222Rn. Deep highly saline groundwater had a radiocarbon concentration typically below 10 pMC. The values of delta13C(DIC) are around-5 per thousand. As delta13C of the aquifer rock samples (Permian, Zechstein carbonates) was in the range of-6...+5 per thousand, residence time corrections based on delta13C are questionable. Additional checks with 39Ar, as well as results from the variationof delta18O (or deltaD) with respect to the salinity, emphasise a Holocene age; as is also the case for most mineralised groundwaters and also for water having a low delta18O (and deltaD). For saline groundwater residing in the Zechstein aquifer the measured delta34S values of about 12 per thousand are close to those expected from the literature. In contrast, the 87Sr/86Sr ratio of dissolved strontium is far from the values anticipated for the aquifer rocks despite there being proportionality between the chloride concentration and the strontium concentration. Furthermore, the proportionality is not valid in lower mineralised water. The 87Sr/86Sr ratio can, therefore, hardly be used as a tracer for the distribution of ascending saline water. The amount of salt-water coming from below into the residual quarry basins is an essential contribution to the lake inventories. Therefore, 222Rn was used to assist in determining the renewal of salt-water layers that formed in deep lake locations. In the deep zones 222Rn concentrations up to 6 Bq/l were measured but were dominantly in equilibrium with 226Ra, which was found in all higher mineralised groundwater samples. Excess radon was limited to just a few decimetres above the lake sediment surface but does not appear to be caused by continuous groundwater discharge. Hydrochemical investigations of groundwater from the Quaternary aquifer were carried out over the last six years before flooding was complete. Apart from a slight downward shift of the average sulfate concentration, other changes showed virtually no trends. An increase of the sulfate concentration was mostly correlated with a decrease of delta34S for individual sites only, but not for the whole ensemble of sampling locations. Sulfate from pyrite oxidation plays an important role but cannot be attributed unequivocally to coal mining. There are hints that the conditions closer to the basin edges may differ from those remoter parts of the flood plain.

Polycyclic aromatic hydrocarbons fluxes during the past 50 years observed in dated sediment cores from Andean mountain lakes in central south Chile.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment; they are of concern due to their toxic properties. Anthropogenic activities could contribute in a significant way to the total burden of PAHs in remote mountain areas. In this work, we document the analysis of PAHs deposition through sedimentary records obtained in three remote Andean lakes located in south central Chile. Sediment cores were taken in one of the deepest sections of each lake, ranging from 45 to 135 m depth. Sediments were carefully extruded in 1-cm layers for PAHs and dating analysis (210Pb and 137Cs). Sixteen Environmental Protection Agency prioritary PAHs were analyzed using high-performance liquid chromatography with fluorescence detection. Dating of sediments was possible for only two lakes (Laja and Galletue). The superficial composition of PAHs in each lake is rather similar with a characteristic dominance of perylene; levels ranged 355 to 3050 ng g(-1) d.w. Depositional fluxes averaged 118 microg m2 year(-1) in Laja Lake in contrast to that in Galletue Lake, where average fluxes reach 434 microg m2 year(-1). Dating back to 50 years, PAH profiles did not experience drastic changes despite the rapid development of industrialization over the past 30 years in the surrounding region, indicating that levels and composition remains fairly similar to those of the present. Finally, determined fluxes were in the lower range of depositional fluxes calculated for lakes located in the industrialized northern hemisphere.

PAH fluxes in the Laja Lake of south central Chile Andes over the last 50 years: evidence from a dated sediment core.

This paper reports the occurrence of polyaromatic hydrocarbons (PAHs) deposition inferred from a sediment core of an Andean lake in south central Chile. Sediments were carefully collected from one of the deepest section of the lake and sliced every 1 cm. The samples were analyzed for PAHs, (137)Cs, (210)Pb, organic carbon and grain-size. The stratigraphic chronology and the sedimentation rates were estimated using the sedimentary signature left by the (137)Cs and (210)Pb fallout as temporal markers. PAHs were quantified by HPLC-fluorescence detection (HPLC-Fluorescence). 15 priority EPA PAHs were analyzed in this study. Based on these results, PAH deposition over the last 50 years was estimated (a period characterized by an important intervention in the area). PAH concentration ranged from 226 to 620 ng g(-1) d.w. The highest concentrations of PAHs were found in the core's bottom. The PAH profile is dominated by the presence of perylene indicating a natural source of PAH. In addition, two clear PAH deposition periods could be determined: the most recent with two-four rings PAHs, the older one with five-seven rings predomination. Determined fluxes where 71 to 972 microg m(-2) year(-1), dominated by perylene deposition. PAH levels and fluxes are lower compared to the levels found in sediments from remote lakes in Europe and North America. It is concluded that the main source of PAHs into the Laja Lake sediments are of natural origin.