Isotope tracing of submarine groundwater discharge offshore Ubatuba, Brazil: results of the IAEA–UNESCO SGD project

Results of groundwater and seawater analyses for radioactive (³H, ²²²Rn, ²²³Ra, ²²⁴Ra, ²²⁶Ra, and ²²⁸Ra) and stable (D and ¹⁸O) isotopes are presented together with in situ spatial mapping and time series ²²²Rn measurements in seawater, direct seepage measurements using manual and automated seepage meters, pore water investigations using different tracers and piezometric techniques, and geoelectric surveys probing the coast. This study represents first time that such a new complex arsenal of radioactive and non-radioactive tracer techniques and geophysical methods have been used for simultaneous submarine groundwater discharge (SGD) investigations. Large fluctuations of SGD fluxes were observed at sites situated only a few meters apart (from 0 cm d⁻¹ to 360 cm d⁻¹; the unit represents cm³/cm²/day), as well as during a few hours (from 0 cm d⁻¹ to 110 cm d⁻¹), strongly depending on the tidal fluctuations. The average SGD flux estimated from continuous ²²²Rn measurements is 17 ± 10 cm d⁻¹. Integrated coastal SGD flux estimated for the Ubatuba coast using radium isotopes is about 7 × 10³ m³ d⁻¹ per km of the coast. The isotopic composition (δD and δ¹⁸O) of submarine waters was characterised by significant variability and heavy isotope enrichment, indicating that the contribution of groundwater in submarine waters varied from a small percentage to 20%. However, this contribution with increasing offshore distance became negligible. Automated seepage meters and time series measurements of ²²²Rn activity concentration showed a negative correlation between the SGD rates and tidal stage. This is likely caused by sea level changes as tidal effects induce variations of hydraulic gradients. The geoelectric probing and piezometric measurements contributed to better understanding of the spatial distribution of different water masses present along the coast. The radium isotope data showed scattered distributions with offshore distance, which imply that seawater in a complex coast with many small bays and islands was influenced by local currents and groundwater/seawater mixing. This has also been confirmed by a relatively short residence time of 1–2 weeks for water within 25 km offshore, as obtained by short-lived radium isotopes. The irregular distribution of SGD seen at Ubatuba is a characteristic of fractured rock aquifers, fed by coastal groundwater and recirculated seawater with small admixtures of groundwater, which is of potential environmental concern and has implications on the management of freshwater resources in the region.     

Comparison between the accumulation capacity of four lichen species transplanted to a urban site

The capacity to accumulate trace elements from the atmosphere of the lichens Hypogymnia physodes, Parmelia sulcata, Pseudevernia furfuracea and Usnea gr. hirta transplanted to an urban site of N Italy was compared. Twenty-nine elements (Al, As, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, Fe, Hg, I, K, La, Mg, Mn, Ni, Pb, Rb, Sb, Sc, Se, Sm, Th, Ti, V, Zn) were analyzed by Instrumental Neutron Activation Analysis (INAA) and Electro-Thermal Atomic Absorption Spectroscopy (ET-AAS). The ratio between the concentrations of each element in exposed samples to that of control samples (exposed-to-control ratio and EC ratio) was used to investigate the accumulation rates of lichen thalli. The results showed that in general elements did not exhibit well defined trends, but rather showed fluctuations, and indicated that H. physodes, P. furfuracea and U. gr. hirta have a similar accumulation capacity, while that of P. sulcata is lower.     

Cellular evaluation of the toxicity of combustion derived particulate matter: influence of particle grinding and washing on cellular response

There is increasing interest in continual monitoring of air for the presence of inhalation health hazards, such as particulate matter, produced through combustion of fossil fuels. Currently there are no means to rapidly evaluate the relative toxicity of materials or to reliably predict potential health impact due to the complexity of the composition, size, and physical properties of particulate matter. This research evaluates the feasibility of utilizing cell cultures as the biological recognition element of an inhalation health monitoring system. The response of rat lung type II epithelial (RLE-6TN) cells to a variety of combustion derived particulates and their components has been evaluated. The focus of the current work is an evaluation of how particles are delivered to a cellular sensing array and to what degree does washing or grinding of the particles impacts the cellular response. There were significant differences in the response of these lung cells to PM's of varying sources. Mechanical grinding or washing was found to alter the toxicity of some of these particulates; however these effects were strongly dependent on the fuel source. Washing reduced toxicity of oil PM's, but had little effect on those from diesel or coal. Mechanical grinding could significantly increase the toxicity of coal PM's, but not for oil or diesel.     

Vanadium recovery from oil fly ash by leaching, precipitation and solvent extraction processes

In order to reduce the environmental impact due to land disposal of oil fly ash from power plants and to valorize this waste material, the removal of vanadium was investigated using leaching processes (acidic and alkaline treatments), followed by a second step of metal recovery from leachates involving either solvent extraction or selective precipitation. Despite a lower leaching efficiency (compared to sulfuric acid), sodium hydroxide was selected for vanadium leaching since it is more selective for vanadium (versus other transition metals). Precipitation was preferred to solvent extraction for the second step in the treatment since: (a) it is more selective; enabling complete recovery of vanadate from the leachate in the form of pure ammonium vanadate; and (b) stripping of the loaded organic phase (in the solvent extraction process) was not efficient. Precipitation was performed in a two-step procedure: (a) aluminum was first precipitated at pH 8; (b) then ammonium chloride was added at pH 5 to bring about vanadium precipitation.     

Heterogeneous photocatalytic degradation of prometryn in aqueous solutions under UV-Vis irradiation

In this study, the heterogeneous photocatalytic degradation of prometryn using TiO(2) as photocatalyst was investigated. The main objectives of the study were: (I) to evaluate the kinetics of the pesticide disappearance, (II) to compare the photocatalytic efficiency of two different types of TiO(2), (III) to examine the influence of various parameters such as initial concentration of pesticide or catalyst and presence of oxidants (H(2)O(2) and K(2)S(2)O(8)), (IV) to evaluate the degree of mineralization and (V) to assess the detoxification efficiency of the studied processes. The experiments were carried out in a 500 ml pyrex UV reactor equipped with a 125 W high-pressure mercury lamp surrounded by a pyrex filter blocking wavelengths below 290 nm. Prometryn concentration was determined using HPLC. It was found that the degradation of the pesticide follows the first order kinetics according to the Langmuir-Hinshelwood model. Parameters like the type and concentration of the catalyst affect the degradation rate. A synergistic effect was observed when an oxidant was added in the TiO(2) suspensions increasing the reaction rate of photodegradation. In order to examine the extent of pesticide mineralization, DOC measurements were carried out. After 6h of illumination, mineralization was achieved up to almost 70%. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fisheri, in order to compare the acute toxicity of prometryn and its photoproducts. The detoxification efficiency was found to be dependent on the studied system and it did not follow the rate of pesticide disappearance.     

Temporal and spatial distributions of sediment total organic carbon in an estuary river

Understanding temporal and spatial distributions of naturally occurring total organic carbon (TOC) in sediments is critical because TOC is an important feature of surface water quality. This study investigated temporal and spatial distributions of sediment TOC and its relationships to sediment contaminants in the Cedar and Ortega Rivers, Florida, USA, using three-dimensional kriging analysis and field measurement. Analysis of field data showed that large temporal changes in sediment TOC concentrations occurred in the rivers, which reflected changes in the characteristics and magnitude of inputs into the rivers during approximately the last 100 yr. The average concentration of TOC in sediments from the Cedar and Ortega Rivers was 12.7% with a maximum of 22.6% and a minimum of 2.3%. In general, more TOC accumulated at the upper 1.0 m of the sediment in the southern part of the Ortega River although the TOC sedimentation varied with locations and depths. In contrast, high concentrations of sediment contaminants, that is, total polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), were found in sediments from the Cedar River. There was no correlation between TOC and PAHs or PCBs in these river sediments. This finding is in contradiction to some other studies which reported that the sorption of hydrocarbons is highly related to the organic matter content of sediments. This discrepancy occurred because of the differences in TOC and hydrocarbon source input locations. It was found that more TOC loaded into the southern part of the Ortega River, while almost all of the hydrocarbons entered into the Cedar River. This study suggested that the locations of their input sources as well as the land use patterns should also be considered when relating hydrocarbons to sediment TOC.     

Long term changes in the eutrophication process in a shallow Mediterranean lake ecosystem of W. Greece: response after the reduction of external load

Lake Pamvotis is a shallow Mediterranean lake located in Western Greece near the city of Ioannina. The lake has been recognized as an internationally important conservation site under European Community legislation due to its rich biodiversity. However, during the last three decades the trophic status of the lake has changed as a result of anthropogenic activity (among others irrigation and domestic sewage discharge), resulting in serious problems. Here we present data about the long-term development in eutrophication of Lake Pamvotis. Water samples were collected and analyzed (water temperature, pH, dissolved oxygen, nutrients, chlorophyll-a) during three monitoring periods: 1985-1989, 1998-1999, 2004-2005. The high nutrient concentrations in the lake water during the three monitoring periods, as well as its eutrophic to hypertrophic status reflect the degree of impact anthropogenic activity has had on the lake. Commencement of a restoration plan in 1995-1996, involving sewage diversion, led to a reduction in external nutrient load and consequently to lower in-lake nutrients and Chlorophyll-a concentrations. Orthophosphate concentration decreased by about 87%, nitrates fell below 1.20mg/l, whilst the total reduction of inorganic N compounds showed a weaker downward trend, fluctuating between 0.39 and 1.24mg N/l with an average value of 0.76mg N/l. However, after a short-term recovery the eutrophic status of the lake remains eight years later (2004-2005), suggesting the importance of the internal loading process and the absence of the top-down effect of fish. This study provides evidence for the need of greater restoration efforts utilized in Mediterranean shallow lakes.     

Lichen and moss bags as monitoring devices in urban areas. Part II: trace element content in living and dead biomonitors and comparison with synthetic materials

Lobes of the lichen Pseudevernia furfuracea (L.) Zopf and shoots of the moss Hypnum cupressiforme Hedw. were subjected to different treatments (water washing, oven drying, HNO3 washing, NH4-oxalate extraction) to assess the influence of vitality on accumulation efficiency, during a 6-week exposure in bags in two Italian cities, Trieste and Naples. No trend emerged between treatments, in terms of accumulation ability, for major and trace elements. Only water-washed lichens showed an increased C and N content after exposure in both cities. Element concentrations generally reached higher values in mosses than in lichens, especially for Al, Fe, and Zn (both cities), and for Cu, Mg and Na (Naples). Surface development strongly influenced accumulation capacity of the biomonitors. Quartzose and cation exchange filters revealed, on a weight basis, a poor performance. In urban environments, surface interception of atmospheric particulate seems to play a major role in accumulation, irrespective of organism vitality.     

Occurrence and fate of pesticides in four contrasting agricultural settings in the United States

Occurrence and fate of 45 pesticides and 40 pesticide degradates were investigated in four contrasting agricultural settings--in Maryland, Nebraska, California, and Washington. Primary crops included corn at all sites, soybeans in Maryland, orchards in California and Washington, and vineyards in Washington. Pesticides and pesticide degradates detected in water samples from all four areas were predominantly from two classes of herbicides--triazines and chloroacetanilides; insecticides and fungicides were not present in the shallow ground water. In most samples, pesticide degradates greatly exceeded the concentrations of parent pesticide. In samples from Nebraska, the parent pesticide atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] was about the same concentration as the degradate, but in samples from Maryland and California atrazine concentrations were substantially smaller than its degradate. Simazine [6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine], the second most detected triazine, was detected in ground water from Maryland, California, and Washington. Metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] rarely was detected without its degradates, and when they were detected in the same sample metolachlor always had smaller concentrations. The Root-Zone Water-Quality Model was used to examine the occurrence and fate of metolachlor at the Maryland site. Simulations accurately predicted which metolachlor degradate would be predominant in the unsaturated zone. In analyses of relations among redox indicators and pesticide variance, apparent age, concentrations of dissolved oxygen, and excess nitrogen gas (from denitrification) were important indicators of the presence and concentration of pesticides in these ground water systems.     

Analysis of pollution status of River Illo,Ota, Nigeria

An assessment of the pollution status of River Illo, located within River Owo catchments area in Ota, Ogun State, Nigeria, was carried out. The River’s response to deoxygenation due to BOD loading from an abattoir and its dissolved oxygen (DO) level was predicted using the modified Streeter-Phelps model. The average concentrations of measured parameters at the sampling stations include: 2.24 mg/l of DO, 312.85 mg/l of BOD, 782.86 mg/l of chemical oxygen demand, and 620.76 g/l of total solids. The DO model for River Illo showed a positive correlation between measured and calculated DO, while the dissolved oxygen curve gave a double spoon shape of two major segments with distinct zones of degradation, decomposition, and recovery. The self-purification factor (f) for both segments ranged between 0.8 and 1.1 depicting River Illo as a slow moving or sluggish river. The above results revealed slow reaeration of the water body while full recovery from pollution was difficult. The treatment of River Illo before usage is very essential to ensure public health safety of users from waterborne diseases.