Partitioning of perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) between water and sediment

Laboratory partitioning experiments were conducted to elucidate the sorption behaviour and partitioning of perfluoroalkyl compounds (PFCs). Three different sediment types were used and separately spiked with perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) at low environmentally realistic concentrations. PFOA, PFOS and PFOSA were mainly distributed in the dissolved phase at low suspended solid concentrations, indicating their long-range transport potential in the marine environment. In all cases, the equilibrium isotherms were linear and the organic carbon normalised partition coefficients (K_OC) decreased in the following order: PFOSA (log K_OC = 4.1 ± 0.35 cm³ g⁻¹) > PFOS (3.7 ± 0.56 cm³ g⁻¹) > PFOA (2.4 ± 0.12 cm³ g⁻¹). The level of organic content had a significant influence on the partitioning. For the sediment with negligible organic content the density of the sediment became the most important factor influencing the partitioning. Ultimately, data on the partitioning of PFCs between aqueous media and suspended solids are essential for modelling their transport and environmental fate.     

Concentration and chemical speciation for the determination of Cu,Zn, Ni,Pb and Cd from refuse dump soils using the optimized BCR sequential extraction procedure

The optimized BCR sequential extraction procedure (proposed by the Standards, Measurements and Testing Programme (SM&T) of the European Union) was applied to seven topsoil samples from refuse dump sites for the determination of Cu, Zn, Ni, Pb and Cd. The metals were partitioned into four operationally defined chemical fractions: acid extractable, reducible, oxidizable and residual, and analysed using flame atomic absorption spectrophotometry, FAAS. The results were compared with total metal concentrations obtained using HNO₃, HClO₄ and HF digestion procedures. Results for total metal analysis ranged from - 15.55 to 43.45 for Cu, 37.15 to 222.35 for Zn, 5.15 to 12.10 for Ni, 10.30 to 93.05 for Pb and 0.35 to 3.75 for Cd in μgg⁻¹ dry weight. The results of the partitioning study showed that zinc prevailed in the more soluble fractions and was distributed between the acid-extractable (32.4%) and the reducible (40.3%) fractions, whereas Pb was distributed mainly in the reducible fraction. Copper and nickel were predominantly associated with the reducible and residual fractions - 53.4, 33.3 and 51.1, 24.1% respectively. The ranking of the four fractions for the partitioning of cadmium was: reducible > residual > oxidizable > acid extractable. The percentage recovery for all metals when comparing total metal concentration with the fractional sum of the optimized BCR procedure, were of the order: Zn(93%) > Pb(83%) > Cu(78) > Cd > (68%) > Ni(63%).     

广州天河区大气中二噁英年度监测及气固分配规律

对广州天河区大气中二噁英进行年度监测和气固分配模式的研究。结果表明,天河区大气中存在较高浓度的二噁英;低氯代二噁英对毒性当量贡献较大,其主要分布在气相,2,3,4,7,8-PeCDF对毒性当量贡献最大,其贡献超过35%;高氯代二噁英(主要是OCDF、OCDD、1,2,3,4,6,7,8-HpCDF和1,2,3,4,6,7,8-HpCDD)对浓度贡献较大,其主要分布在颗粒相。     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Carbon partitioning among the first trophic levels in the North Western Adriatic Basin

In the frame of PRISMA II Project samples for plankton analyses were carried out during four cruises (June, 1996; February and June, 1997; February, 1998) in order to assess the relative importance in term of biomasses of the three main size fractions (pico- <2 r µm, nano- 2-20 r µm and micro-plankton >20 r µm). Spatial and temporal distribution of the three plankton fractions were described as abundance and contribution to the total carbon content in an area between Po River mouth and Rimini. The relative contribution of picoplankton resulted higher in the offshore zone, while that of nanoplankton in the inshore waters. In February 1998 microphytoplankton, mainly constituted by diatoms, was very abundant in the inshore waters. Micro-zooplankton was always very scarce. Cluster analyses performed on these data grouped the stations on the basis of their community structure, and agreed with the hydrological features. Small size classes contributed more significantly to the total plankton carbon content in most of the situations. Microplankton fraction contribution was relevant only during spring diatom bloom of February 1998 and with a less extent in the confined coastal summer blooms.     

Kinetic and thermodynamic studies on partitioning of polychlorinated biphenyls (PCBs) between aqueous solution and modeled individual soil particle grain sizes

The significance of soil mineral properties and secondary environmental conditions such as pH, temperature, ionic strength and time in the partitioning of eight selected polychlorinated biphenyl(PCB) congeners between aqueous solution and soil particles with different grain sizes was studied. The mineral properties of a model soil sample were determined, and Brunauer–Emmett–Teller(BET) adsorption–desorption isotherms were employed to observe the surface characteristics of the individual modeled soil particles.Batch adsorption experiments were conducted to determine the sorption of PCBs onto soil particles of different sizes. The results revealed that the sorption of PCB congeners onto the soil was dependent on the amount of soil organic matter, surface area, and pore size distribution of the various individual soil particles. Low pH favored the sorption of PCBs,with maximum sorption occurring between pH 6.5 and 7.5 with an equilibration period of 8 hr.Changes in the ionic strength were found to be less significant. Low temperature favored the sorption of PCBs onto the soil compared to high temperatures. Thermodynamic studies showed that the partition coefficient(K_d) decreased with increasing temperature, and negative and low values of ΔH° indicated an exothermic physisorption process. The data generated is critical and will help in further understanding remediation and cleanup strategies for polluted water.     

Can aquatic distribution of human pharmaceuticals be related to pharmacological data?

The recognition of pharmaceuticals as significant environmental contaminants has only been a recent phenomenon. Therefore there is a paucity of data relating to the fate and effects of pharmaceuticals once they enter an aquatic receiving system. The amount of work that needs to be done in terms of risk assessment for pharmaceuticals required by regulatory agencies is substantial. This paper has determined the environmental partitioning coefficient (K_d) of 13 diverse human pharmaceuticals in three model systems of differing combinations of solid phases and solutions. The K_d values were then compared with distribution values of the pharmaceuticals in the human body determined from pharmacological studies. This was done to assess the functional relationship between K_d and distribution values in the human body (V_D). K_d values ranged from 3 to 2450 L kg⁻¹. Regression coefficients ranged from r² = 0.62–0.72, indicating that V_D values are a useful indicator for the K_d values of the tested pharmaceuticals within the batch sorption systems. The relationship between K_d and V_D should therefore be further explored to determine whether this relationship can be applied to a broader range of pharmaceuticals in more diverse environmental systems. Exploiting available human pharmacological data in such a way would be of great benefit in prioritising human pharmaceuticals as environmental contaminants in the risk assessment process.     

Development of a continuously stirred flow cell for investigating sorption mass transfer

This paper introduces a new reversible-flow design for a continuously stirred reactor used to study sorption mass transfer in soil and solvent systems. The stirred reactor has potential advantages over conventional packed column or batch reactors because it isolates intraparticle sorption rate limitations from advective-dispersive transport, yet allows changes to flux through the reactor for analysis of sorption kinetics under dynamic conditions. Previously, stirred reactors have often failed due to clogging of sediment on the effluent frit. The reverse-flow backwashing design allows longer life and higher confidence in maintaining mixed conditions than previous designs. Mass transfer 'rate coefficients estimated from stirred and column experiments are compared; both techniques produced results consistent with a published correlation. The data also show that fitted sorption mass transfer coefficients can be strongly dependent on the choice of equilibrium partition coefficient (i.e. batch or first-moment derived values), and that the conventional two-site sorption kinetics model fails to accurately predict sorption mass transfer in the presence of changing solvent velocity through the reactor.     

Transport of volatile compounds in porous media in the presence of a trapped gas phase

The presence of an immobile gaseous phase in an otherwise-saturated porous medium affects the transport of volatile compounds. The linear theory of partitioning tracers suggests that a volatile tracer introduced into such a system should be retarded with a constant retardation factor. Using high concentrations, however, the saturation of the gaseous phase will change as an effect of the tracer test itself. Competitive gas transfer among all volatile compounds and the change of saturation may lead to tracer concentrations that are temporarily higher than those injected. We analyze the system in the framework of the coherence theory by Helfferich [Soc. Pet. Eng. J. 21 (1) (1981) 51]. The governing equations are formulated as functions of total concentration, i.e., the mass of solutes in all phases per pore volume. Neglecting dispersion and mass-transfer kinetics, we derive the characteristic form of the resulting system of hyperbolic equations. In a system with N volatile compounds, a variation of the concentrations splits up into N waves, each traveling with its own characteristic velocity. If the presence of a gaseous phase is sustained, one wave will be a standing one. We perform numerical model calculations for tracers with various Henry's law coefficients and show that the results agree with the semi-analytical solution obtained by coherence theory.     

Copper mobilization affected by weather conditions in a stormwater detention system receiving runoff waters from vineyard soils (Champagne, France)

Copper, a priority substance on the EU-Water Framework Directive list, is widely used to protect grapevines against fungus diseases. Many vineyards being located on steep slopes, large amounts of Cu could be discharged in downstream systems by runoff water. The efficiency of stormwater detention basins to retain copper in a vineyard catchment was estimated. Suspended solids, dissolved (Cu_diss) and total Cu (Cu_tot) concentrations were monitored in runoff water, upstream, into and downstream from a detention pond. Mean Cu_tot concentrations in entering water was 53.6 μg/L whereas it never exceeded 2.4 μg/L in seepage. Cu_tot concentrations in basin water (>100 μg/L in 24% of the samples) exceeded LC₅₀ values for several aquatic animals. Copper was principally sequestered by reduced compounds in the basin sediments (2/3 of Cu_tot). Metal sequestration was reversible since sediment resuspension resulted in Cu remobilization. Wind velocity controlled resuspension, explained 70% of Cu_diss variability and could help predicting Cu mobilization.