Inventory and vertical migration of 90Sr fallout and 137Cs/90Sr ratio in Spanish mainland soils

In this paper the inventory of ⁹⁰Sr in 34 points distributed along the Spanish peninsular territory is presented. Obtained values range between 173 Bq/m² and 2047 Bq/m². From these data set and those ¹³⁷Cs data obtained in a previous work the ¹³⁷Cs/⁹⁰Sr activity ratio has been established, laying this value between 0.9 and 3.6. Also the migration depth of both radionuclides has been analysed obtaining for ¹³⁷Cs an average value 57% lower than that obtained for ⁹⁰Sr.Additionally, this paper presents the results obtained in 11 sampling points in which the activity vertical profile has been measured. These profiles have been analysed to state the behaviour of strontium in soils and after, by using a convective-diffusive model, the parameters of the model which governs the vertical migration of ⁹⁰Sr in the soil, v (apparent convection velocity) and D (apparent diffusion coefficient) have been evaluated. Mean values obtained are 0.20 cm/year and 3.67 cm²/year, respectively.     

Sorption of selenate on soils and pure phases: kinetic parameters and stabilisation

This study was conducted to identify the principle selenate carrier phases for two selected soils, by comparing their reactivity with selenate to that of pure phases of the solids. Silica, calcium carbonate, aluminium hydroxide, goethite, bentonite and humic acid were selected as the main soil carrier phases. Comparisons were made first on the parameter values obtained with the best fit of a kinetic sorption model which can discriminate instantaneous sorption from kinetically limited sorption. Then comparisons were made of the ability for each solid to stabilise selenate by measuring the ratio of the partition coefficient for sorption (Kd_sorption) over that of the desorption (Kd_desorption). Kinetics and stabilisation were used to help elucidate the nature of interactions with the test solid phases for a large range of selenate concentrations. The experiments were conducted over 165 h in batch reactors, the solid being isolated from the solution by dialysis tubing, at two pH (5.4 and 8) and three selenate concentrations (1 × 10⁻³, 1 × 10⁻⁶ and 1 × 10⁻⁸ mol L⁻¹). The results obtained showed that only aluminium hydroxide can sorb selenate throughout the studied pH range (pH 5.4 to 8.0). The sorption capacity on this mineral was high (Kd_sorption > 100 to 1 × 10⁴ L kg⁻¹) and the selenate was mainly stabilized by the formation of inner sphere complexes. The sorption on goethite occurred at pH 5.4 (Kd_sorption 52 L kg⁻¹), mainly as outer sphere complexes, and was null at pH 8. On silica, a weak sorption was observed only at pH 5.4 and at 165 h (Kd_sorption 4 L kg⁻¹). On bentonite, calcium carbonate and humic acid no significant sorption was observed. Concerning the two soils studied, different behaviours were observed for selenate. For soil Ro (pH 5.4), Kd_sorption was low (8 L kg⁻¹) compared to soil Bu (pH 8) (70 L kg⁻¹). The sorption behaviour of selenate on soil Ro was mainly due to outer sphere complexes, as for goethite, whereas for soil Bu the sorption was mainly attributed to inner sphere complexes followed by reduction mechanisms, probably initiated by microorganisms, in which no steady state was reached at the end of the 165 h experiments. The sorption of selenate decreased when concentrations reached 1 × 10⁻³ mol L⁻¹, due to solid saturation, except for aluminium hydroxide. Reduction of selenate seemed also to occur on goethite and soil Ro, for the same concentration, but without preventing a decrease in sorption. Thus, this work shows that the comparison of selenate behaviour between soil and pure phases helps to elucidate the main carrier phases and sorption mechanisms in soil.     

Soil and biodiversity

It is shown that the soil diversity-biodiversity system in terrestrial ecosystems operates in spatiotemporal unity, which manifests itself at different hierarchical levels of their structural-functional organization: successional-evolutionary, zonal geographic, landscape, biogeocenotic, soil-type, horizon-layer, geochemical, and the levels of elementary soil processes and soil fertility. Arguments confirming the functional relationship between organisms and soils are considered. Effective biodiversity conservation is possible on the basis of an ecosystems approach involving simultaneous conservation of soil diversity.     

Assessment of Uncertainty in Long-Term Mass Balances for Acidification Assessments: A MAGIC Model Exercise

Long-term (1860–2010) catchment mass balance calculations rely on models and assumptions which are sources of uncertainty in acidification assessments. In this article, we report on an application of MAGIC to model acidification at the four Swedish IM forested catchments that have been subject to differing degrees of acidification stress. Uncertainties in the modeled mass balances were mainly associated with the deposition scenario and assumptions about sulfate adsorption and soil mass. Estimated base cation (BC) release rates (weathering) varied in a relatively narrow range of 47–62 or 42–47 meq m⁻² year⁻¹, depending on assumptions made about soil cation exchange capacity and base saturation. By varying aluminum solubility or introducing a dynamic weathering feedback that allowed BC release to increase at more acidic pHs, a systematic effect on predicted changes in acid neutralizing capacity (ΔANC ca. 10–41 μeq l⁻¹) and pH (ca. ΔpH = 0.1–0.6) at all sites was observed. More robust projections of future changes in pH and ANC are dependent on reducing uncertainties in BC release rates, the timing, and extent of natural acidification through BC uptake by plants, temporal changes in soil element pools, and fluxes of Al between compartments.     

Integrated biological responses of zebrafish (Danio rerio) to analyze water quality in regions under anthropogenic influence

This study analyzed water quality in regions around Patos lagoon (Southern Brazil) that are under anthropogenic pressure. Water samples were collected from five different sites, including one used as a source for human consumption (COR) and others known to be influenced by human activities (IP). Danio rerio (Teleostei, Cyprinidae) organisms were exposed for 24 h to these water samples, plus a control group. It was observed that: (1) reactive oxygen species levels were lower in COR and IP than in the control group; (2) glutamate-cysteine ligase (catalytic subunit) expression was higher in COR than in other sites; (3) exposure to all water samples affected long-term memory (LTM) when compared to control group. Thus, some water samples possess the ability to modulate the antioxidant system and to induce a decline in cognitive functions, as measured by LTM. The obtained results indicate that a combination of variables of different organization level (molecular, biochemical and behavioral) can be employed to analyze water quality in impacted regions.     

Engineered nanomaterials in rivers--exposure scenarios for Switzerland at high spatial and temporal resolution

Probabilistic material flow analysis and graph theory were combined to calculate predicted environmental concentrations (PECs) of engineered nanomaterials (ENMs) in Swiss rivers: 543 river sections were used to assess the geographical variability of nano-TiO₂, nano-ZnO and nano-Ag, and flow measurements over a 20-year period at 21 locations served to evaluate temporal variation. A conservative scenario assuming no ENM removal and an optimistic scenario covering complete ENM transformation/deposition were considered. ENM concentrations varied by a factor 5 due to uncertain ENM emissions (15%-85% quantiles of ENM emissions) and up to a factor of 10 due to temporal river flow variations (15%-85% quantiles of flow). The results indicate highly variable local PECs and a location- and time-dependent risk evaluation. Nano-TiO₂ median PECs ranged from 11 to 1′623 ng L⁻¹ (conservative scenario) and from 2 to 1′618 ng L⁻¹ (optimistic scenario). The equivalent values for nano-ZnO and nano-Ag were by factors of 14 and 240 smaller.     

Can arbuscular mycorrhizal fungi improve grain yield, As uptake and tolerance of rice grown under aerobic conditions?

The effects of arbuscular mycorrhizal fungi (AMF) - Glomus intraradices and G. geosporum on arsenic (As) and phosphorus (P) uptake by lowland (Guangyinzhan) and upland rice (Handao 502) were investigated in soil, spiked with and without 60 mg As kg⁻¹. In As-contaminated soil, Guangyinzhan inoculated with G. intraradices or Handao 502 inoculated with G. geosporum enhanced As tolerance, grain P content, grain yield. However, Guangyinzhan inoculated with G. geosporum or Handao 502 inoculated with G. intraradices decreased grain P content, grain yield and the molar ratio of grain P/As content, and increased the As concentration and the ratio of grain/straw As concentration. These results show that rice/AMF combinations had significant (p < 0.05) effects on grain As concentration, grain yield and grain P uptake. The variation in the transfer and uptake of As and P reflected strong functional diversity in AM (arbuscular mycorrhizal) symbioses.     

Functional redundancy and food web functioning in linuron-exposed ecosystems

An extensive data set describing effects of the herbicide linuron on macrophyte-dominated microcosms was analysed with a food web model to assess effects on ecosystem functioning. We showed that sensitive phytoplankton and periphyton groups in the diets of heterotrophs were gradually replaced by more tolerant phytoplankton species as linuron concentrations increased. This diet shift--showing redundancy among phytoplankton species--allowed heterotrophs to maintain their functions in the contaminated microcosms. On an ecosystem level, total gross primary production was up to hundred times lower in the treated microcosms but the uptake of dissolved organic carbon by bacteria and mixotrophs was less sensitive. Food web efficiency was not consistently lower in the treated microcosms. We conclude that linuron predominantly affected the macrophytes but did not alter the overall functioning of the surrounding planktonic food web. Therefore, a risk assessment that protects macrophyte growth also protects the functioning of macrophyte-dominated microcosms.     

Bromination of selected pharmaceuticals in water matrices

The bromination of five selected pharmaceuticals (metoprolol, naproxen, amoxicillin, phenacetin, and hydrochlorothiazide) was studied with these compounds individually dissolved in ultra-pure water. The apparent rate constants for the bromination reaction were determined as a function of the pH, obtaining the sequence amoxicillin > naproxen ? hydrochlorothiazide ≈ phenacetin ≈ metoprolol. A kinetic mechanism specifying the dissociation reactions and the species formed for each compound according to its pK_a value and the pH allowed the intrinsic rate constants to be determined for each elementary reaction. There was fairly good agreement between the experimental and calculated values of the apparent rate constants, confirming the goodness of the proposed reaction mechanism.In a second stage, the bromination of the selected pharmaceuticals simultaneously dissolved in three water matrices (a groundwater, a surface water from a public reservoir, and a secondary effluent from a WWTP) was investigated. The pharmaceutical elimination trend agreed with the previously determined rate constants. The influence of the main operating conditions (pH, initial bromine dose, and characteristics of the water matrix) on the degradation of the pharmaceuticals was established. An elimination concentration profile for each pharmaceutical in the water matrices was proposed based on the use of the previously evaluated apparent rate constants, and the theoretical results agreed satisfactorily with experiment. Finally, chlorination experiments performed in the presence of bromide showed that low bromide concentrations slightly accelerate the oxidation of the selected pharmaceuticals during chlorine disinfection.     

Sociodemographic, reproductive and dietary predictors of organochlorine compounds levels in pregnant women in Spain

Organochlorine pesticides and polychlorinated biphenyls (PCBs) are consistently found in human tissues. Serum levels of organochlorine compounds (OC) in pregnant women in particular have raised concern about possible harm to humans in the early phases of physical and behavioural development. The objective of the present study was to evaluate the association between concentration of OCs in serum of two cohorts of pregnant women from Gipuzkoa and Sabadell in Spain and socioeconomic, reproductive and dietary variables. Concentration of polychlorinated biphenyls (PCBs: 28, 52, 101, 118, 138, 153 and 180), hexachlorobenzene (HCB), beta and gamma-hexachlorocyclohexane (β-HCH and γ-HCH), heptachlor epoxide, dichlorodiphenyl dichloroethylene (p,p'-DDE) and dichlorodiphenyl trichloroethane (p,p'-DDT) were measured in the serum of 1259 pregnant women. Associations between OCs and potential predictor variables were assessed using linear regression models adjusted for potential confounders. The compounds most commonly found in the serum were p,p'-DDE (99% of the samples) and PCB-153 (95% of the samples). Geometric means of serum concentrations (ng g?1 lipid) of organochlorine pesticides were 110.0, 19.1, and 33.5 for p,p'-DDE, β-HCH, and HCB respectively, while the geometric means of PCBs were 21.8, 38.9 and 26.9 for PCB 138, 153, and 180 respectively. The levels of all OCs increased with age. BMI was positively associated with the concentration of organochlorine pesticides but inversely related to PCB concentrations. The serum levels of OCs fell only after a cumulative period of breastfeeding of over a year. Levels of PCBs were related to fish intake, but in general dietary factors did not improve the explained variability of the concentrations of OCs. Overall, the levels of OCs found in the study are at the lower end of the range reported in Spain and other countries.