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A previously developed potential cleanup tool for atrazine contaminated soils was evaluated in larger open soil microcosms for optimization under more realistic conditions, using a natural crop soil spiked with an atrazine commercial formulation (Atrazerba FL). The doses used were 20x or 200x higher than the recommended dose (RD) for an agricultural application, mimicking over-use or spill situations. Pseudomonas sp. strain ADP was used for bioaugmentation (around 10(7) or 10(8) viable cells g(-1) of soil) and citrate for biostimulation (up to 4.8 mg g(-1) of soil). Bioremediation treatments providing fastest and higher atrazine biodegradation proved to differ according to the initial level of soil contamination. For 20x RD of Atrazerba FL, a unique inoculation with Pseudomonas sp. ADP (9 +/- 1 x 10(7) CFU g(-1)) resulted in rapid atrazine removal (99% of the initial 7.2 +/- 1.6 microg g(-1) after 8d), independent of citrate. For 200x RD, an inoculation with the atrazine-degrading bacteria (8.5 +/- 0.5 x 10(7) CFU g(-1)) supplemented with citrate amendment (2.4 mg g(-1)) resulted in improved biodegradation (87%) compared with bioaugmentation alone (79%), even though 7.8 +/- 2.1 microg of atrazine g(-1) still remained in the soil after 1 wk. However, the same amount of inoculum, distributed over three successive inoculations and combined with citrate, increased Pseudomonas sp. ADP survival and atrazine biodegradation (to 98%, in 1 wk). We suggest that this bioremediation tool may be valuable for efficient removal of atrazine from contaminated field soils thus minimizing atrazine and its chlorinated derivatives from reaching water compartments.

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A presença de bisfenol A e de isômeros do 4-nonilfenol, compostos que promovem desequilíbrio do sistema endócrino, foi determinada em amostras de águas superficiais de Portugal. O método analítico envolveu a preconcentração de 200 mL de água, utilizando extração por fase sólida com cartuchos OASIS, seguida de análise por cromatografia gasosa acoplada a espectrometria de massas.As recuperações e os limites de detecção do bisfenol A e dos isômeros do 4-nonilfenol foram 119 % e 73 %, respectivamente e 0,002 µg L -1 e 0,01 µg L -1 . O método foi aplicado na determinação destes poluentes em águas de rios e costeiras por um período de três meses (agosto-outubro/1999). O total de amostras analisadas foi 135. As concentrações de bisfenol A e dos isômeros do 4-nonilfenol variaram de 0,2 a 4,0 µg L -1 e 0,2 a 30 µg L -1 , respectivamente. Somente em duas amostras de água de rios, a concentração dos isômeros de 4-nonilfenol ultrapassou 10 µg L -1 e do bisfenol A 2 µg L -1 . Concentrações superiores a estes valores podem causar efeitos estrogênicos em peixes.The occurrence of the endocrine disruptor compounds, such as 4-nonylphenol isomers and bisphenol A was determined in surface water samples from Portugal. The analytical method used involved the preconcentration of 200 mL of water sample by solid phase extraction (SPE) using a OASIS (Waters) cartridge, followed by Gas Chromatography-Mass Spectrometry (GC/MS) determination. Recoveries and limits of detection of 4-nonylphenol isomers and bisphenol-A were 73 % and 119 %, respectively, 0.01 µg L -1 and 0.002 µg L -1 . The method was applied to the determination of these estrogenic pollutants in river and coastal waters during three months (AugustOctober/1999). The total samples analyzed were 135. Concentrations of 4-nonylphenol isomers and bisphenol-A ranged from 0.03-30 µg L -1 and 0.07-4.0 µg L -1 , respectively. Only in two river samples, concentrations of 4-nonylphenol isomers were above 10 µg L -1 and bisphenol-A were above 2 µg L -1 . These values can cause estrogenic effects in fish and these sampling points require further investigation in order to verify the maintenance of these levels.

Forty polybrominated diphenyl ethers (PBDEs), from mono- through hepta-brominated, were analyzed in river and coastal sediment samples of the eight main river basins of Portugal to investigate the occurrence, geographical distribution, and detailed congener profiles. Thirty-two sediment samples taken along the different rivers from inland to the open sea revealed an increase toward the river mouth with a total PBDE concentration of 20 ng/g-dw, and levels decreased to 0.5 ng/g-dw in coastal sediments. PBDEs were detected in all samples analyzed, indicating a diffuse source of pollution in the aquatic environments. Maximum levels were encountered in sediments collected close to urban and industrial areas. Of 40 congeners included in the analytical work, 17 congeners were detected in river sediments. BDE 47 was found in all samples analyzed whereas BDEs 100 and 99 were found in more than 26 out of 32 samples analyzed at concentrations from 0.03 to 10 ng/g-dw. This study is unique in showing the presence of previously nondescribed lower brominated PBDEs in riverine and marine sediments. BDEs 7, 11, 12+13, 15, 30, 32, 17, 25, 28+33, 49, 75, and 71 were identified in two to five samples with a median of 0.03−0.55 ng/g-dw. The analytical method developed consisted of the use of Soxhlet extraction with a novel cleanup method employing alumina cartridges and analysis by gas chromatography−mass spectrometry operated in negative chemical ionization mode.

Purpose To mitigate the environmental effects of atrazine, one of the cleanup strategies available is based on the use of atrazine-degrading bacteria. This work aimed to evaluate the efficacy of a previously developed bioremediation tool for atrazine-contaminated soils (combining bioaugmentation with Pseudomonas sp. ADP, hereafter designated as P. ADP, and biostimulation with citrate) on both soil habitat and retention functions, by performing ecotoxicological tests with standard soil and aquatic species. Materials and methods Soil microcosms (incorporating earthworms, collembolans, and plants) were spiked with three doses of Atrazerba FL, an atrazine commercial formulation: the recommended dose (RD; 2 L/ha), 10×RD and 20×RD to simulate overuse/accidental spills scenarios. The experiment included two main groups of treatments:(1) microcosms sprayed solely with Atrazerba, i.e., nonbioremediated soils (NB) and (2) microcosms sprayed with both Atrazerba and the bioremediation tool (addition of P. ADP plus citrate), i.e., bioremediated soils (B). Control microcosms with no herbicide or P. ADP plus citrate addition were also set up. Besides soil chemical analysis, the following ecotoxicological endpoints were assessed to monitor bioremediation: plant biomass production, earthworm reproduction, microalgae growth (in eluatescollected 5 and 10 days after the bioremediation treatmentand leachates-collected on day seven), and cladoceran reproduction (in soil eluates). Results In NB soils, all Atrazerba doses induced a severe reduction in plant biomass production, and no effects were found for earthworm's reproduction. Eluates and leachates obtained from the NB soils caused deleterious effects on both microalgae growth and cladoceran reproduction. Chemical analysis showed that atrazine degradation was faster in B soils than in the correspondent NB soils. Data from toxicity tests indicated that test organism performance was enhanced in B soils and respective eluates and leachates, compared to the NB samples. In fact, for soils contaminated with 10 and 20×RD Atrazerba doses, plant biomass production was significantly higher in the B soils than in the correspondent NB soils. Regarding the effects of soil bioremediation on the toxicity of soil eluates and leachates, for the soil contaminated with 10 ×RD of Atrazerba, over a 5-day treatment period, both microalgae growth and cladoceran reproduction were significantly higher in water extracts obtained from the B soils when compared with the NB extracts and also similar to the control. By the contrary, for the highest Atrazerba dose tested (20×RD), no significant differences were found on the toxicity of B and NB eluates toward both aquatic test organisms. However, for this same dose, after 7 days, microalgae growth was higher in B than in the NB leachates and similar to the control. Yet, after a longer bioremediation period of 10 days, eluates were also no longer toxic to both aquatic organisms. Discussion Based on atrazine soil chemical analysis, one can state that the addition ...