Development,validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water,soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L^?1, and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L^?1), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L^?1 and 20.4, 9.0, 21.6, and 13.0 ng L^?1, respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L^?1 and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg^?1), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg^?1), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg^?1). The relative standard deviation for the recovery of pesticides was under 15%.     

Nitrogen deposition effects on Mediterranean-type ecosystems: an ecological assessment

We review the ecological consequences of N deposition on the five Mediterranean regions of the world. Seasonality of precipitation and fires regulate the N cycle in these water-limited ecosystems, where dry N deposition dominates. Nitrogen accumulation in soils and on plant surfaces results in peaks of availability with the first winter rains. Decoupling between N flushes and plant demand promotes losses via leaching and gas emissions. Differences in P availability may control the response to N inputs and susceptibility to exotic plant invasion. Invasive grasses accumulate as fuel during the dry season, altering fire regimes. California and the Mediterranean Basin are the most threatened by N deposition; however, there is limited evidence for N deposition impacts outside of California. Consequently, more research is needed to determine critical loads for each region and vegetation type based on the most sensitive elements, such as changes in lichen species composition and N cycling.     

Pentachlorophenol association with fulvic acids from recycled wastes

The apparent water solubility of pentachlorophenol was measured at pH=6 and at 25 degrees C in pure water, aqueous solutions of three salts (NaCl, KNO(3) and CaCl(2) at 0.010, 0.10 and 1.0M) and in aqueous solutions of three fulvic acids samples extracted from a natural soil (sFA), composted sewage sludge (csFA) and composted livestock's material (lsFA). A solubility enhancement method was developed for the measurement of partition coefficients (K(oc), L/kg organic carbon). Pentachlorophenol associates strongly with the fulvic acid samples and the calculated K(oc) were the following (averages and standard deviations): (sFA) (211+/-22) x 10(2), (csFA) (253+/-26) x 10(2), (lsFA) (235+/-10) x 10(2). For comparison purposes the K(oc) for pyrene were also calculated for the three FA samples and were the following: (sFA) (119+/-10) x 10(2), (csFA) (239+/-21) x 10(2), (lsFA) (92+/-10) x 10(2). The analysis of variance (one-way ANOVA) of the effect of the type of FA sample on the solubilization of pentachlorophenol and pyrene shows that this factor causes significant differences on the aqueous solubilization of these two organic substances.     

Discriminating the pH toxicity to Poecilia reticulata Peters, 1859 in the Dunas Lake (Camaçari, BA, Brazil)

Toxic potential of the pH reduction to fingerlings of Poecilia reticulata, through acute toxicity bioassays, as well as the influence of increased pH on the toxicity were assessed. Acid lake samples (Dunas Lake) were collected during 19 months, and assessed with following treatments: water at local pH (+/-3.0) and samples with modified pH to 3.5, 3.8, 4.0, 4.3, 4.6, 5.0, 5.5, 6.0, and 6.5. Culture water samples with pH reduced to 3.0 were also assessed. Newborn P. reticulata were exposed during 96h, and dead/immobile organisms were counted at various time intervals during exposure (short intervals in the beginning and long towards the end). Mean results of LT(50) and confidence intervals from the Dunas Lake and control water with reduced pH were 1.36 (+/-0.48)h, and 1.03 (+/-0.50)h, respectively, with no statistical difference. Samples with increased pH showed a significant reduction in toxicity, with no toxicity detected at pH 6.0 and higher. Relationship between pH and lethal toxicity for fingerlings of P. reticulata demonstrated that pH exerted a strong effect on the survival of this species at the Dunas Lake, explaining about 80% of the toxicity observed.     

Relationships between nutrients and macroalgal biomass in a brazilian coastal lagoon: the impact of a lock construction

The Piratininga Lagoon is a coastal, choked, and brackish ecosystem in SE Brazil, where uncontrolled discharge of domestic sewage led to eutrophication, increasing massive proliferation of benthic macroalgae, and decrease of the lagoon mean depth. In 1992, a dam was constructed by the local Municipality at its tidal channel aiming at stabilising its water level. Main physico-chemical parameters, together with macroalgae biomass, nutrient concentrations in the water column, particulate organic carbon, and chlorophyll a were recorded monthly at 4 sampling stations within the Piratininga lagoon from April 1994 to April 1995. The data, compared with “before-lock” existing studies, show that nutrients and chlorophyll a concentrations significantly increased after the lock construction. Based on the functioning of the ecosystem, we propose to harvest the algal mats before their decomposition period in order to partly remove the nutrient stocks from the lagoon and the future ecosystem modelling to predict the impact of natural and anthropogenic eutrophication.     

Effects of hand weeding strip and nitrogen fertilizer on corn plants

The objective of the present research was to evaluate effects of different strip weed control associated with nitrogen fertilizer on corn applied after planting. The experiment was set and conducted in Botucatu, S?o Paulo State, Brazil, and the hybrid planted was Dekalb 333-B. A completely randomized block design with four replications was used. Experimental plots were disposed as a factorial scheme 2 x 2 x 4, constituted by two types of weeding on row (with or without manual hoeing), two types of weeding on inter-row (with or without manual hoeing), and four nitrogen levels applied after planting (00, 60, 90, and 120 kg ha(-1)). Plots were composed by six rows with 5 m length. Nitrogen fertilizer was applied at 35 days after emergence (d.a.e). For weed community it was evaluated: weed density, dominancy, frequency, and relative importance. The main weed species were: Brachiaria plantiginea, Amaranthus retroflexus, Bidens pilosa, Cyperus rotunds, Brachiaria decumbens, Euphorbia heterofila, Oxalis latifolia, Acanthospermum hispidum, Commelina benghalensis. It was evaluated corn height at 40 and 100 d.a.e., first ear insertion height at 100 d.a.e., and final grain yield at harvesting. Plants and first ear insertion height were affected when nitrogen fertilizer was not applied. Treatments without weed control showed that weed interfered negatively with plants height. There were no correlation between weeds and nitrogen fertilizer for all parameters evaluated. Parcels without weed showed the highest ear weights and final grain production. Treatments that received nitrogen fertilizer, independently of studied arrangement, provided higher yields.     

Linking marine resources to ecotonal shifts of water uptake by terrestrial dune vegetation

As evidence mounts that sea levels are rising, it becomes increasingly important to understand the role of ocean water within terrestrial ecosystem dynamics. Coastal sand dunes are ecosystems that occur on the interface of land and sea. They are classic ecotones characterized by zonal distribution of vegetation in response to strong gradients of environmental factors from the ocean to the inland. Despite the proximity of the dune ecosystem to the ocean, it is generally assumed that all vegetation utilizes only freshwater and that water sources do not change across the ecotone. Evidence of ocean water uptake by vegetation would redefine the traditional interpretation of plant-water relations in the dune ecosystem and offer new ideas for assessing maritime influences on function and spatial distribution of plants across the dune. The purpose of this study was to identify sources of water (ocean, ground, and rain) taken up by vegetation using isotopic analysis of stem water and to evaluate water uptake patterns at the community level based on the distribution and assemblage of species. Three coastal dune systems located in southern Florida, USA, and the Bahamian bank/platform system were investigated. Plant distributions across the dune were zonal for 61-94% of the 18 most abundant species at each site. Species with their highest frequency on the fore dune (nearest the ocean) indicate ocean water uptake as evidenced by delta 18O values of stem water. In contrast, species most frequent in the back dune show no evidence of ocean water uptake. Analysis of species not grouped by frequency, but instead sampled along a transect from the ocean toward the inland, indicates that individuals from the vegetation assemblage closest to the ocean had a mixed water-harvesting strategy characterized by plants that may utilize ocean, ground-, and/or rainwater. In contrast, the inland vegetation relies mostly on rainwater. Our results show evidence supporting ocean water use by dune vegetation and demonstrate an exciting relationship between seawater and ecotonal shifts in plant function of a terrestrial ecosystem.     

In situ and laboratory bioassays using Poecilia reticulata Peters, 1859 in the biomonitoring of an acidic lake at Camaçari, BA, Brazil

The suitability and viability of acute in situ bioassays were investigated in the biomonitoring program of an acidic lake contaminated with sulphur residues. Responses of organisms observed in laboratory and in situ bioassays were also assessed to determine whether or not they were similar and comparable, regarding accuracy and precision. Newborn Poecilia reticulata were employed as test organisms and exposed to the same water samples under in situ and laboratory conditions. Mortality/immobility was the endpoint assessed and dead/immobile organisms were counted at various time intervals during exposure. The mean calculated LT50 values and 95% confidence intervals were 1.61 (1.36-1.87) h in the laboratory bioassays and 0.72 (0.55-0.89) h in the in situ bioassays. Statistical comparison of these values revealed a significant difference (p<0.05). In situ bioassays were more accurate than those carried out in the laboratory, demonstrating higher sensitivity and better reproduction of what occurs in nature, while laboratory bioassays were more precise.     

Radon exhalation from phosphogypsum building boards: symmetry constraints, impermeable boundary conditions and numerical simulation of a test case

Comprehensive understanding of (222)Rn exhalation from phosphogypsum-bearing building material and its accumulation in indoor air is likely to rely on numerical simulation, particularly if transient effects, three-dimensional domains and convection are to be included and investigated. Yet, experimental data and analytical results are helpful (if not crucial) as far as validation is concerned. Having in mind computational code simplicity and in the light of a recent experimental and theoretical report on (222)Rn release from phosphogypsum boards for housing panels, this paper presents and discusses an alternative testing set-up and the corresponding boundary conditions, namely one side of the panel bounded by impermeable wall. Although this is a new facility to be tested, the resultant steady-state one-dimensional diffusion-dominant analytical solution is shown to match the counterpart deduced in the aforementioned previous report, despite it relaxes the constraint of symmetry about the phosphogypsum board centerline, which is inferred in that prior experimental scenario. In addition, numerical results are conducted for a diffusion-dominant two-dimensional time-varying test case concerning (222)Rn accumulation in a closed chamber having an exhaling phosphogypsum board tightly placed at one wall.