Analysis of chlorothalonil and degradation products in soil and water by GC/MS and LC/MS

We present a method using gas chromatography (GC) and liquid chromatography (LC) coupled to a mass selective detector to measure concentrations of the fungicide chlorothalonil and several of its metabolites in soil and water. The methods employed solid-phase extraction using a hydrophobic polymeric phase for the isolation of analytes. In lake water, average analyte recoveries ranged from 70% to 110%, with exception of pentachloronitrobenzene that gave low recoveries (23%). The method detection limits were determined to be in the range of 1 and 0.1microg l(-1) for the LC and GC methods, respectively. In soil samples, recoveries ranged from 80% to 95% for 4-hydroxy-2,5,6-trichloroisophthalonitrile (metabolite II) and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene (metabolite III). Limits of detection (LOD) were 0.05 and 0.02microg g(-1), respectively. Chlorothalonil and other metabolites were analyzed by GC giving recoveries ranging from 54% to 130% with LOD of 0.001-0.005microg g(-1).     

Economic,equitable, and affordable adaptations to protect coastal settlements against storm surge inundation

The distribution of risk of coastal inundation, and the potential benefits of adapting to protect against inundation, vary greatly both within and between coastal communities. This diversity is a result of physical factors, such as the risk of storm surge, sea level rise projections, and the topography of the landscape, as well as socio-economic factors, such as the level of development, and the capacity within the community to adapt. Despite this strong local variation, various communities share common characteristics that constrain or enable different adaptation options in different situations. Understanding these drivers is likely to be important in engaging coastal communities in the discussion around adaptation and may provide new insights into which adaptation options are suitable for each of our at-risk coastal communities. We performed a property-level analysis of 6 suburb-sized case studies distributed along the coast of Queensland, Australia. We assessed the potential economic costs of inundation events now and in the future under sea level rise projections, and the potential avoided costs following adaptation to protect against inundation. We went beyond this to estimate the distribution of risk in each community and compared the potential costs of adaptation with the capacity of the community to pay for their implementation. We used these insights to propose a typology of coastal communities based on their exposure to total inundation risk, the distribution of that risk within the community, and their capacity to adapt.     

Migration of As, Hg, Pb, and Zn in arroyo sediments from a semiarid coastal system influenced by the abandoned gold mining district at El Triunfo, Baja California Sur, Mexico

Extensive waste deposits (tailings) and ash from the ignition oven of the abandoned gold mine of mining district El Triunfo (MD-ET) in Baja California Sur, Mexico have released trace elements into the sediments of the Hondo-Las Gallinas-El Carrizal arroyo, which connects to the Pacific Ocean through an evaporitic basin. Migration of these elements through the arroyo is mainly caused by winds or tropical hurricanes that occur sporadically during the summer and cause the otherwise dry arroyo to overflow. To evaluate the concentration and distribution of the elements As, Hg, Pb, and Zn along the 48 km arroyo, surface sediments were collected from 26 sites, ranging from close to the MD-ET to the mouth of the arroyo at the Pacific Ocean. Concentrations in tailings and ash were for As 8890 and 505?000 mg kg(-1); for Hg 0.336 and 54.9 mg kg(-1); for Pb 92,700 and 19,300 mg kg(-1); and for Zn 49,600 and 1380 mg kg(-1). The average of the Normalized Enrichment Factor (Av-NEF) in surface sediments, calculated using background levels, indicates that the sediments are severely contaminated with As and Zn (Av-NEF = 22), Pb (Av-NEF = 24) and with a moderate contamination of Hg (Av-NEF = 7.5). The anthropogenic influence of those elements is reflected in the arroyo sediments as far as 18 km away from the MD-ET, whereas the samples closest to the discharge into the Pacific Ocean show a natural to moderate enrichment for As and Zn and low or no enrichment for Hg and Pb. A principal components analysis identified four principal components that explained 90% of the total variance. Factor 1 was characterized by a high positive contribution of the anthropogenic source elements, especially As, Pb, and Zn (37%), whereas Factor 2 was strongly correlated with the oxy-hydroxides of Fe and Mn (27%). Factor 3 was correlated with Li (16%) and Factor 4 with Al (10%), which indicates more than one source of lithogenic composition, though they played a minor role in the distribution of the elements.     

Large male advantage for access to females: evidence of male-male competition and female discrimination in a territorial salamander

Summary In the natural habitat visited in this study, adult male red-backed salamanders (Plethodon cinereus) found near females were significantly larger than adult males found alone; there was no evidence for size assortative associations. Previous research has indicated that females associate preferentially with males that occupy high quality territories and that larger individuals are more successful at obtaining higher quality areas. In laboratory experiments, when resource quality was held constant and males were restrained so that male-male interactions were prohibited, females discriminated behaviorally between large and small males by spending more time visually and chemically assessing larger males and more time apparently attempting to leave the chamber when near smaller males. Females were found near the larger males at the end of the trials significantly more often than predicted by chance. In a separate experiment in which only females were restrained, larger males spent significantly more time in aggressive postures when paired with smaller males than when alone with the female. Smaller males spent significantly more time in submissive postures when paired with larger males and more time near the female when alone. Therefore, large body size of males may positively affect both intra- and intersexual interactions and, ultimately, mating success of male P. cinereus.     

Agricultural pesticide residues of farm runoff in the Okanagan Valley,British Columbia,Canada

The objectives of this study were to determine environmental occurrence and concentrations of selected currently-used-pesticides and some transformation products in agricultural farms in the Okanagan Valley (OKV), and to conduct a simple risk assessment of environmental pesticides levels detected in OKV on non-target aquatic organisms. The OKV is the tree fruit country of the Province of British Columbia where considerable amount of pesticides are applied annually. Water, sediment and soil samples were collected at eleven sites in early June and late September following rainfall events and/or extended periods of irrigation from drainage ditches and/or from small streams. Undisturbed reference sites were also sampled. Study results showed that forty of the eighty chemicals analyzed, including organochlorine, nitrogen-containing and organophosphate pesticides commonly used for OKV crops, were detected in runoff and small stream water samples. Among which, endosulfan-sulfate was the most frequently detected chemical. Also, azinophos-methyl (0.699–25.5 ng/L), diazinon (0.088–214 ng/L) exceeded, and α-, β- endosulfan, endosulfan sulphate approached the guidelines for the protection of aquatic life.     

Impacts of Dams on Flow Regimes in Three Headwater Subbasins of the Columbia River Basin,United States1

Moore, Johnnie N., Alicia S. Arrigoni, and Andrew C. Wilcox, 2012. Impacts of Dams on Flow Regimes in Three Headwater Subbasins of the Columbia River Basin, United States. Journal of the American Water Resources Association (JAWRA) 48(5): 925‐938. DOI: 10.1111/j.1752‐1688.2012.00660.x Abstract: We compared long‐term changes in flow regimes resulting from climate change with those resulting from dams in three matched pairs of natural and modified headwater subbasins of the Columbia River. Based on the analysis of 12 flow‐regime metrics, we found that damming had minimal effect on most quantity of flow metrics, but major effect on timing of flow metrics, especially those representing “spring runoff.” In all modified subbasins, “spring runoff” metrics occurred much earlier than natural flow (up to ～44 days earlier for April‐July flows). Storage capacity modulated the magnitude of timing of flow‐metric changes, with the largest storage capacity leading to the most change. However, even in subbasins with low storage capacity, we found significant change in most timing of flow metrics. We also found that damming, especially in subbasins with higher storage capacity, overwhelmed climate variability in all basins for most flow metrics. This shows that reservoir operations need to be modified to more closely match the natural timing of flow regimes to promote positive ecologic response in modified rivers, even in basins where quantity of flow metrics have not changed substantially as a result of damming.     

Volatile carbonylic compounds in downtown Santiago, Chile

Formaldehyde, acetaldehyde, acetone, propanal, butanal, 2-butenal, 3-methylbutanal, hexanal, benzaldehyde, 2-methylbenzaldehyde, and 2,5-dimethylbenzaldehyde were measured during six spring days at downtown Santiago de Chile. Measurements were performed 24h/day and averaged over three hour periods. The averages of the maxima (ppbv) were, formaldehyde: 3.9+/-1.4; butanal: 3.3+/-3.4; acetaldehyde: 3.0+/-0.9; acetone: 2.4+/-1.0; 2-butenal: 0.56+/-0.52; propanal: 0.46+/-0.21; benzaldehyde: 0.34+/-0.3; 3-butanal: 0.11+/-0.05; hexanal: 0.11+/-0.08; 2-methylbenzaldehyde: 0.08+/-0.05; 2,5-dimethylbenzaldehyde: 0.05+/-0.03. Aliphatic aldehydes (C1-C3) are strongly correlated among them and weakly with primary (toluene) and secondary (ozone plus nitrogen dioxide or PAN) pollutants. In particular, the correlation between acetaldehyde and propanal values remains even if diurnal and nocturnal data are considered separately, indicating similar sources. All these aldehydes present maxima values in the morning (9-12h) and minima at night (0-3h). The best correlation is observed when butanal and 2-butenal data are considered (r=0.99, butanal/2-butenal=6.2). These compounds present maxima values during the 3-6h period, with minima values in the 0-3h period. These data imply a strong pre-dawn emission. Other aldehydes show different daily profiles, suggesting unrelated origins. Formaldehyde is the aldehyde whose concentration values best correlate with the levels of oxidants. The contribution of primary emissions and photochemical processes to formaldehyde concentrations were estimated by using a multiple regression. This treatment indicates that (32+/-16)% of measured values arise from direct emissions, while (79+/-23)% is attributable to secondary formation.     

Kinetic model for phenolic compound oxidation by Fenton's reagent

A kinetic model is developed for the oxidation of phenolic compounds by Fenton's reagent. In the first stage a rigorous kinetic model is applied to calculate the different kinetic rate constants for the oxidation process of p-hydroxybenzoic acid. In a second phase a competitive method is applied to calculate these kinetic constants for another 10 phenolic compounds present in agroindustrial and pulp paper wastewaters. These 10 phenolic compounds were: beta-resorcylic acid, 3-(4-hydroxyphenyl)-propionic acid, ferulic acid, protocatechuic acid, caffeic acid, p-coumaric acid, vanillic acid, syringic acid, veratric acid and 3,4,5-trimethoxybenzoic acid.     

Aquatic macrophytes potential for the simultaneous removal of heavy metals (Buenos Aires, Argentina)

Heavy metal removal from water has been approached by using different technologies. Phytotechnologies, with an increasing development during the last two decades, involve using plants for metal removal. Three autochthonous floating macrophytes, common in pampean shallow lakes (Argentina), Pista stratiotes, Spirodela intermedia and Lemna minor were used in laboratory experiences for the simultaneously removal of several heavy metals (Fe, Cu, Zn, Mn, Cr and Pb) resulting from anthropogenic activity, in order to simulate a naturally polluted environment. The experiences were performed for different concentrations of metals along 15 days. High metal removal percentages were obtained for the 3 species and metals. L. minor did not survive the conditions of the experiment. High correlation between the final water and the macrophytes metal concentration was obtained, deviations were due to PbCrO(4) precipitation. The rate of metal uptake was dependent on the metal concentration for the 3 species studied.