Estilita Ruiz-Romera

Non-target effects of three formulated pesticides on microbially-mediated processes in a clay-loam soil

An experiment was performed to study non-target effects of difenoconazole (fungicide), deltamethrin (insecticide) and ethofumesate (herbicide) on microbial parameters in a clay-loam soil. Pesticides were applied as commercial formulations to soil samples at different concentrations (5, 50 and 500 mg kg(-1) DW soil) and then incubated under laboratory conditions for 3 months. Throughout the incubation period, microbial parameters were determined at days 7, 30, 60 and 90. At 5 mg kg(-1) DW soil, none of the three pesticides caused significant changes in soil microbial parameters. In contrast, at 500 mg kg(-1) DW soil, pesticide application decreased overall soil microbial activity, negatively affecting the activity of soil enzymes. Similarly, at 500 mg kg(-1) DW soil, difenoconazole and ethofumesate, but not deltamethrin, caused a pesticide-induced stress on soil microbial communities, as reflected by the respiratory quotient. Besides, deltamethrin and ethofumesate at 50 and 500 mg kg(-1) DW soil resulted in lower values of denitrification potential. It was concluded that, although pesticide concentration had a somewhat inconsistent and erratic effect on soil microbial parameters, pesticide application at 500 mg kg(-1) DW soil did have an impact on many of the microbial parameters studied here.

Influence of anthropogenic inputs and a high-magnitude flood event on metal contamination pattern in surface bottom sediments from the Deba River urban catchment

The purpose of this study was to assess the influence of anthropogenic factors (infrastructure construction and industrial and wastewater inputs) and hydrological factors (high-magnitude flood events) on metal and organic contamination and on the source variability of sediments taken from the Deba River and its tributaries. The pollution status was evaluated using a sequential extraction procedure (BCR 701), enrichment factor, individual and global contamination factors and a number of statistical analysis methods. Zn, Cu and Cr were found to have significant input from anthropogenic sources, with moderately severe enrichment, together with an extremely high potential risk of contamination. The principal scavenger of Cu and Cr was organic matter, whereas Zn was uniformly distributed among all non-residual fractions. For Fe, the anthropogenic contribution was more obviously detected in bulk sediments (<2 mm) than in fine fractions (<63 μm). Finally, the recent construction of a rail tunnel traversing Wealden Facies evaporites, together with intense rainfalls, was the main reason for the change in the source variability of bottom sediments and metal distribution in headwaters. The occurrence of a high-magnitude flood event resulted in a washout of the river bed and led to a general decrease in fine-grained sediment and metal concentrations in labile fractions of channel-bottom sediments, and a consequent downstream transfer of the pollution.

Monitoring heavy metal concentrations in leachates from a forest soil subjected to repeated applications of sewage sludge

The aim of the study was to establish whether the repeated application of sewage sludge to an acid forest soil (Dystric Cambisol) would lead to short-term groundwater contamination. Sludge was applied at four loading rates (0, 2.4, 17 and 60 Mg ha(-1)) in two consecutive years and leachates were analysed. Heavy metal inputs to soils at the lowest dose were below EC regulations but, at higher doses, limits for Zn, Cd, Cr and Ni were exceeded. Repeated application of sludge at 60 Mg ha(-1) resulted in significantly (P<0.05) higher concentrations of Zn, Cd, Cr and Ni in the leachates than with other treatments. The drinking water standards for Cd and Ni were surpassed in all treatments. Control plots were contaminated by groundwater flow despite the existence of buffer zones between plots. This complicated interpretation of the results, highlighting the importance of careful design of this type of experiment.

Nitrogen transformations and greenhouse gas emissions from a riparian wetland soil: an undisturbed soil column study.

Riparian wetlands bordering intensively managed agricultural fields can act as biological filters that retain and transform agrochemicals such as nitrate and pesticides. Nitrate removal in wetlands has usually been attributed to denitrification processes which in turn imply the production of greenhouse gases (CO(2) and N(2)O). Denitrification processes were studied in the Salburua wetland (northern Spain) by using undisturbed soil columns which were subsequently divided into three sections corresponding to A-, Bg- and B2g-soil horizons. Soil horizons were subjected to leaching with a 200 mg NO₃⁻L⁻¹ solution (rate: 90 mL day⁻¹) for 125 days at two different temperatures (10 and 20°C), using a new experimental design for leaching assays which enabled not only to evaluate leachate composition but also to measure gas emissions during the leaching process. Column leachate samples were analyzed for NO₃⁻concentration, NH(4)(+) concentration, and dissolved organic carbon. Emissions of greenhouse gases (CO₂ and N₂O) were determined in the undisturbed soil columns. The A horizon at 20°C showed the highest rates of NO₃⁻ removal (1.56 mg N-NO₃⁻kg⁻¹ DW soil day⁻¹) and CO₂ and N₂O production (5.89 mg CO₂ kg⁻¹ DW soil day⁻¹ and 55.71 μg N-N₂O kg⁻¹ DW soil day⁻¹). For the Salburua wetland riparian soil, we estimated a potential nitrate removal capacity of 1012 kg N-NO₃⁻ha⁻¹ year⁻¹, and potential greenhouse gas emissions of 5620 kg CO₂ ha⁻¹ year⁻¹ and 240 kg N-N₂O ha⁻¹ year⁻¹.

Deltamethrin degradation and soil microbial activity in a riparian wetland soil.

The effects of deltamethrin, in the presence and absence of nitrate, on soil microbial activity (as reflected by the rates of soil microbial basal respiration, denitrification, and methanogenesis) were studied in a riparian wetland soil under both aerobic and anaerobic conditions. A microcosm study was carried out with soil collected from the vicinity of a wetland. The soil was then amended with 50, 125, and 250 mg deltamethrin kg−1 dry weight soil, in the presence and absence of 20 mg N-NO3− kg−1 dry weight soil. Half-life values for deltamethrin degradation ranged from 27 to 291 days, depending on experimental conditions. Nitrates had an inhibitory effect on deltamethrin degradation. Deltamethrin, under anaerobiosis, had an inhibitory effect on soil respiration; this effect was reversed in the presence of nitrate. An antagonistic effect between deltamethrin degradation and denitrification activity was observed. In the presence of nitrate, the activation of denitrifying bacteria led to competitive inhibition of methanogens. It was concluded that deltamethrin, designed to affect specific functions of its target organisms, also has an effect on nontarget organisms, that is, the soil microbial community. To our knowledge, this is the first report on the degradation and environmental impact of deltamethrin in a riparian wetland soil.

Changes in heavy metal concentrations in acid soils under pine stands subjected to repeated applications of biosolids.

The distribution of metals in biosolid-amended soils (as measured by acid extraction) to a depth of 53 cm was examined for evidence of translocation and possible redeposition and to determine whether downward-moving heavy metals interacted with the subsoil. The soil is a sandy acid forest soil (Dystric Cambisol) located in a high-leaching environment. The biosolid was applied twice (in 2001 and 2002) at three different loading rates, and soils were sampled in the 3 years following the first application (2002, 2003, and 2004). Zinc, chromium, nickel, and copper accumulated in the uppermost horizon (0- to 4-cm depth), and the highest concentrations corresponded to the highest doses of biosolids. The lack of cadmium accumulation in this horizon was attributed to the high mobility of this element. Between 4 and 9 cm to the 48-cm depth, and with few exceptions, there were no significant differences (P < 0.05) between the different doses of biosolids and control. The existence of both subsurface lateral flow and preferential flow may explain the lack of differences. Cadmium mainly accumulated at 48 to 53 cm, which was the depth of the water table. At this depth, an overall increase in the concentrations of the other heavy metals was also observed. This pattern was attributed to the longer time of contact between the soil-reactive surface and soil solution.

Chemical and physiological metal bioaccessibility assessment in surface bottom sediments from the Deba River urban catchment: Harmonization of PBET, TCLP and BCR sequential extraction methods

In the present study, the physiologically based extraction test PBET (gastric and intestinal phases) and two chemical based extraction methods, the toxicity characteristic leaching procedure (TCLP) and the sequential extraction procedure BCR 701 (Community Bureau of Reference of the European Commission) have been used to estimate and evaluate the bioaccessibility of metals (Fe, Mn, Zn, Cu, Ni, Cr and Pb) in sediments from the Deba River urban catchment. The statistical analysis of data and comparison among physiological and chemical methods have highlighted the relevance of simulate the gastrointestinal tract environment since metal bioaccessibility seems to depend on water and sediment properties such as pH, redox potential and organic matter content, and, primordially, on the form in which metals are present in the sediment. Indeed, metals distributed among all fractions (Mn, Ni, Zn) were the most bioaccessible, followed by those predominantly bound to oxidizable fraction (Cu, Cr and Pb), especially near major urban areas. Finally, a toxicological risk assessment was also performed by determining the hazard quotient (HQ), which demonstrated that, although sediments from mid- and downstream sampling points presented the highest metal bioaccessibilities, were not enough to have adverse effects on human health, Cr being the most potentially toxic element.

Effect of flood events on transport of suspended sediments, organic matter and particulate metals in a forest watershed in the Basque Country (Northern Spain).

An understanding of the processes controlling sediment, organic matter and metal export is critical to assessing and anticipating risk situations in water systems. Concentrations of suspended particulate matter (SPM), dissolved (DOC) and particulate (POC) organic carbon and metals (Cu, Ni, Pb, Cr, Zn, Mn, Fe) in dissolved and particulate phases were monitored in a forest watershed in the Basque Country (Northern Spain) (31.5km(2)) over three hydrological years (2009-2012), to evaluate the effect of flood events on the transport of these materials. Good regression was found between SPM and particulate metal concentration, making it possible to compute the load during the twenty five flood events that occurred during the study period at an annual scale. Particulate metals were exported in the following order: Fe>Mn>Zn>Cr>Pb>Cu>Ni. Annual mean loads of SPM, DOC and POC were estimated at 2267t, 104t and 57t, respectively, and the load (kg) of particulate metals at 76 (Ni), 83 (Cu), 135 (Pb), 256 (Cr), 532 (Zn), 1783 (Mn) and 95170 (Fe). Flood events constituted 91%-SPM, 65%-DOC, 71%-POC, 80%-Cu, 85%-Ni, 72%-Pb, 84%-Cr, 74%-Zn, 87%-Mn and 88%-Fe of total load exported during the three years studied. Flood events were classified into three categories according to their capacity for transporting organic carbon and particulate metals. High intensity flood events are those with high transport capacity of SPM, organic carbon and particulate metals. Most of the SPM, DOC, POC and particulate metal load was exported by this type of flood event, which contributed 59% of SPM, 45% of organic carbon and 54% of metals.

Treated and untreated wastewater effluents alter river sediment bacterial communities involved in nitrogen and sulphur cycling

Studying the dynamics of nitrogen and sulphur cycling bacteria in river surface sediments is essential to better understand their contribution to global biogeochemical cycles. Evaporitic rocks settled at the headwater of the Deba River catchment (northern Spain) lead to high values of sulphate concentration in its waters. Besides, the discharge of effluents from untreated and treated residual (urban and industrial) wastewaters increases the concentration of metals, nutrients and organic compounds in its mid- and low-water courses. The aim of this study was to assess the impact of anthropogenic contamination from untreated and treated residual and industrial wastewaters on the structure and function of bacterial communities present in surface sediments of the Deba River catchment. The application of a quantitative functional approach (qPCR) based on denitrification genes (nir: nirS+nirK; and nosZ), together with a 16S rRNA gene metabarcoding structural analysis, revealed (i) the high relevance of the sulphur cycle at headwater surface sediments (as reflected by the abundance of members of the Syntrophobacterales order, and the Sulfuricurvum and Thiobacillus genera) and (ii) the predominance of sulphide-driven autotrophic denitrification over heterotrophic denitrification. Incomplete heterotrophic denitrification appeared to be predominant in surface sediments strongly impacted by treated and untreated effluents, as reflected by the lower values of the nosZ/nir ratio, thus favouring N2O emissions. Understanding nitrogen and sulphur cycling pathways has profound implications for the management of river ecosystems, since this knowledge can help us determine whether a specific river is acting or not as a source of greenhouse gases (i.e., N2O).

Implications of denitrification in the ecological status of an urban river using enzymatic activities in sediments as an indicator

A better understanding of the effects of a number of environmental factors on denitrification is vital for analyzing its role as nitrogen sink and providing deeper knowledge about the ecological status of a nitrate-rich ecosystem. Since few studies have addressed the occurrence and implications of denitrification in river sediments, and complexity of interactions among all these environmental factors makes comprehension of the process difficult, the potential of sediments from the Deba River to attenuate nitrate excess through denitrification was investigated. For this purpose, we adapted an in vitro method to measure activities of two enzymes contributing to the entire multiple-step nitrate reduction: Nitrate Reductase and Nitrite Reductase. The environmental features that influence both or single enzymatic activities were identified as oxygen availability, regulated directly by the moisture content or indirectly through the aerobic respiration, organic matter and nitrate content of sediments, and electrical conductivity and exchangeable sodium percentage of water. Additionally, our results showed that Nitrate Reductase catalyzes the principal limiting step of denitrification in sediments. Therefore, taking this enzymatic activity as an indicator, the southern part of the Deba River catchment presented low potential to denitrify but nitrate-limited sediments, whereas the middle and northern parts were characterized by high denitrification potential but nitrate-rich sediments. In general, this study on denitrifying enzymatic activities in sediments evaluates the suitability of the management of the effluents from wastewater treatment plants and municipal sewages to ensure a good ecological status of the Deba River.