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.     

Partitioning and removal of perfluorooctanoate during rain events: the importance of physical-chemical properties

The potential for airborne emissions to undergo long-range transport or to be removed from the atmosphere is influenced by their physical-chemical properties. When perfluorooctanate (PFO) enters the environment, its physical-chemical properties can vary significantly, depending on whether it exists as an acid, a salt, or a dissociated ion. A summary of the physical-chemical properties of the three most likely environmental states: ammonium perfluorooctanoate (APFO), perfluorooctanoic acid (PFOA) and the dissociated perfluorooctanoate anion (PFO(-)) is presented to illustrate the distinct environmental properties of each. The most volatile species, PFOA, is shown to have a pH-dependent air-water partitioning coefficient (K(aw)). The variability of K(aw) with pH influences the potential for vapor formation from aqueous environments, including rain events. Using the pH-dependent K(aw) and measured rain and air concentrations, it is shown that vapor-phase PFOA is not likely to be present above measurable levels of 0.2 ng m(-3) (12 parts per quadrillion v/v) during a rain event. Because rain concentrations determined in this work are comparable to measurements in other parts of North America, it is unlikely that rain events are a significant source of vapor-phase PFOA for the general North American region. It is shown that PFOA exists primarily in the particle phase in ambient air near direct sources of emissions and is efficiently scavenged by rain droplets, making wet deposition an important removal mechanism for emissions originating as either PFOA or APFO. Washout ratios of particle-associated PFO were determined to range between 1 x 10(5) and 5 x 10(5), in the same range as other semi-volatile compounds for which wet deposition is an important mechanism for atmospheric removal and deposition onto soils and water bodies.     

A closed-chamber CO2-flux method for estimating intertidal primary production and respiration under emersed conditions

This paper describes a closed-chamber method for measuring CO₂ fluxes in intertidal soft sediments during periods of emersion. The method relies on closed-circuit incubations of undisturbed sediment and measurement of CO₂ exchanges using an infrared gas analyser. The method was assessed during field experiments, both in light and dark conditions, on an exposed sandy beach and in an estuary. The rates of gross community production measured under moderate irradiance (4.2 mg C m^-2 h^-1 on the exposed sandy beach and 35 mg C m^-2 h^-1 in the estuary) are in good agreement with rates reported in the literature. In conjunction with appropriate sampling strategies, this method can be useful for estimating and comparing production of intertidal areas or for assessing factors that influence production.     

水体中钼污染物的迁移转化研究进展

水体的重金属钼污染在中国部分地区已经显现,明确钼迁移转化规律是治理钼污染的基础.在总结水体钼污染形成机制的基础上,综述了水体钼污染物迁移转化的研究进展.其中,在水体胶体对钼的吸附研究方面较深入,酸碱条件和胶体种类是钼迁移转化的主要影响因素.而目前的研究,对尾矿中不同种类原钼矿物迁移转化与环境条件相互作用的关系尚不明确.因此,解决实际钼污染同题还需更深入的系统性探索.     

A directional passive air sampler for monitoring polycyclic aromatic hydrocarbons (PAHs) in air mass

A passive air sampler was developed for collecting polycyclic aromatic hydrocarbons (PAHs) in air mass from various directions. The airflow velocity within the sampler was assessed for its responses to ambient wind speed and direction. The sampler was examined for trapped particles, evaluated quantitatively for influence of airflow velocity and temperature on PAH uptake, examined for PAH uptake kinetics, calibrated against active sampling, and finally tested in the field. The airflow volume passing the sampler was linearly proportional to ambient wind speed and sensitive to wind direction. The uptake rate for an individual PAH was a function of airflow velocity, temperature and the octanol-air partitioning coefficient of the PAH. For all PAHs with more than two rings, the passive sampler operated in a linear uptake phase for three weeks. Different PAH concentrations were obtained in air masses from different directions in the field test.     

Risk assessment of trace elements in the stomach contents of Indo-Pacific Humpback Dolphins and Finless Porpoises in Hong Kong waters

The potential health risks due to inorganic substances, mainly metals, was evaluated for the two resident marine mammals in Hong Kong, the Indo-Pacific Humpback Dolphin (Sousa chinensis) and the Finless Porpoise (Neophocaena phocaenoides). The stomachs from the carcasses of twelve stranded dolphins and fifteen stranded porpoises were collected and the contents examined. Concentrations of thirteen trace elements (Ag, As, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Se, V and Zn) were determined by inductively coupled plasma mass spectrometer (ICP-MS). An assessment of risks of adverse effects was undertaken using two toxicity guideline values, namely the Reference Dose (RfD), commonly used in human health risk assessment, and the Toxicity Reference Value (TRV), based on terrestrial mammal data. The levels of trace metals in stomach contents of dolphins and porpoises were found to be similar. Risk quotients (RQ) calculated for the trace elements showed that risks to the dolphins and porpoises were generally low and within safe limits using the values based on the TRV, which are less conservative than those based on the RfD values. Using the RfD-based values the risks associated with arsenic, cadmium, chromium, copper, nickel and mercury were comparatively higher. The highest RQ was associated with arsenic, however, most of the arsenic in marine organisms should be in the non-toxic organic form, and thus the calculated risk is likely to be overestimated.     

A near real-time system for continuously monitoring airborne subtilisin-type enzymes in the industrial atmosphere

We describe the development and validation of a portable system comprising an air sampler coupled to an automated flow injection analysis device. The system is able to monitor airborne concentrations of subtilisin-type enzymes in the workplace atmosphere on a continuous basis. Sampling is in two stages: using a sampling head that is designed to mimic human respiration at approx. 1 m s(-1) at a sampling rate of 600 l min(-1). In the second stage, the captured particles are deposited by impaction from the air stream onto the inner surface of a cyclone that is continuously washed with a jet of buffer solution. Deposited particles are then washed into a reservoir from which samples are taken every 5-6 min and injected automatically into a continuous flow injection analysis system. Proteolytic enzyme in the sample passes through a bioreactor maintained at about 40 degrees C. This contains a cellulose solid phase matrix on which is covalently immobilised Texas Red-labelled gelatin as substrate. The passing enzyme partially digests the substrate releasing fluorophore that is detected down stream in a flow cell coupled to a fluorimeter. The system is calibrated using enzyme standards and the intensity of the resulting peaks from the ex-air samples is converted to airborne concentrations using a mathematical model programmed into a PC. The system has a limit of detection of 4.8 ng m(-3) and a dynamic range of 5-60 ng m(-3). The within assay precision (RSD) is 6.3-9.6% over this range. The within batch precision is 20.3% at 20 ng m(-3) and the corresponding between batch value is 19.5%. The system has been run for periods up to 8 h in the laboratory and for up to 4 h at a factory site and the values obtained compared with time-averaged values obtained from a conventional Galley sampler and in-house analysis when reasonable agreement of the results was observed. The stability of the system over 21 days of continuous use with standards injected periodically was studied. Linearity was observed for all the standard plots throughout. At the end of 21 days, after a total exposure equivalent to 2395 ng ml(-1) of Savinase, the signal due to the 5.0 ng ml(-1) standard was still easily detectable.     

Use of USLE/GIS Methodology for Predicting Soil Loss in a Semiarid Agricultural Watershed

The Universal Soil Loss Equation (USLE) is an erosion model to estimate average soil loss that would generally result from splash, sheet, and rill erosion from agricultural plots. Recently, use of USLE has been extended as a useful tool predicting soil losses and planning control practices in agricultural watersheds by the effective integration of the GIS-based procedures to estimate the factor values in a grid cell basis. This study was performed in the Kazan Watershed located in the central Anatolia, Turkey, to predict soil erosion risk by the USLE/GIS methodology for planning conservation measures in the site. Rain erosivity (R), soil erodibility (K), and cover management factor (C) values of the model were calculated from erosivity map, soil map, and land use map of Turkey, respectively. R values were site-specifically corrected using DEM and climatic data. The topographical and hydrological effects on the soil loss were characterized by LS factor evaluated by the flow accumulation tool using DEM and watershed delineation techniques. From resulting soil loss map of the watershed, the magnitude of the soil erosion was estimated in terms of the different soil units and land uses and the most erosion-prone areas where irreversible soil losses occurred were reasonably located in the Kazan watershed. This could be very useful for deciding restoration practices to control the soil erosion of the sites to be severely influenced.     

Sorption of the veterinary antimicrobials sulfadimethoxine and ormetoprim in soil

Currently, limited research on the fate of antimicrobials in the environment exists, once they are discharged in human and animal wastes. Sorption of two antimicrobials, sulfadimethoxine (SDM) and ormetoprim (OMP), was investigated in two soils and sand using a series of batch experiments. Because OMP and SDM are often administered in combination, their sorption was also investigated in combination as co-solutes. The rate of SDM and OMP sorption was rapid over the first few hours of the experiments, which then slowed considerably after 16 to 68 h. OMP sorption was enhanced at high concentrations when in combination with SDM, with linear sorption coefficients ranging from 1.3 to 58.3 L.kg(-1) in the single solute experiments and 4.96 to 89.7 L.kg(-1) in the co-solute experiments. Sorption of OMP as a single solute seems to provide a better fit with the Freundlich equation, which became more linear (n approached 1) when SDM was present. Overall, SDM sorbed less than OMP in the two soils and sand. SDM linear sorption coefficients ranged from 0.4 to 25.8 L.kg(-1) as a single solute and 2.5 to 22.1 L.kg(-1) as a co-solute. Sorption of SDM becomes more nonlinear (n < 1) when SDM is present in combination with OMP. Overall, sorption of both antimicrobials increased in the selected soils and sand as the organic matter, clay content, and cation exchange capacity increased. These experiments indicate relatively low sorption of SDM and OMP in natural soils, making them a potential threat to surface and ground water.