Modeling the dynamics of DDT in a remote tropical floodplain: indications of post-ban use?

Significant knowledge gaps exist regarding the fate and transport of persistent organic pollutants like dichlorodiphenyltrichloroethane (DDT) in tropical environments. In Brazil, indoor residual spraying with DDT to combat malaria and leishmaniasis began in the 1950s and was banned in 1998. Nonetheless, high concentrations of DDT and its metabolites were recently detected in human breast milk in the community of Lake Puruzinho in the Brazilian Amazon. In this work, we couple analysis of soils and sediments from 2005 to 2014 at Puruzinho with a novel dynamic floodplain model to investigate the movement and distribution of DDT and its transformation products (dichlorodiphenyldichloroethylene (DDE) and dichlorodiphenyldichloroethane (DDD)) and implications for human exposure. The model results are in good agreement with the accumulation pattern observed in the measurements, in which DDT, DDE, and DDD (collectively, DDX) accumulate primarily in upland soils and sediments. However, a significant increase was observed in DDX concentrations in soil samples from 2005 to 2014, coupled with a decrease of DDT/DDE ratios, which do not agree with model results assuming a post-ban regime. These observations strongly suggest recent use. We used the model to investigate possible re-emissions after the ban through two scenarios: one assuming DDT use for IRS and the other assuming use against termites and leishmaniasis. Median DDX concentrations and p,p′-DDT/p,p′-DDE ratios from both of these scenarios agreed with measurements in soils, suggesting that the soil parameterization in our model was appropriate. Measured DDX concentrations in sediments were between the two re-emission scenarios. Therefore, both soil and sediment comparisons suggest re-emissions indeed occurred between 2005 and 2014, but additional measurements would be needed to better understand the actual re-emission patterns. Monte Carlo analysis revealed model predictions for sediments were very sensitive to highly uncertain parameters associated with DDT degradation and partitioning. With this model as a tool for understanding inter-media cycling, additional research to refine these parameters would improve our understanding of DDX fate and transport in tropical sediments.     

Transition to Non-toxic Gunshot Use in Olympic Shooting: Policy Implications for IOC and UNEP in Resolving an Environmental Problem

Olympic shooters discharge, annually, thousands of tons of lead shot which pose toxic risks to animals and may pollute both surface and ground waters. Non-toxic steel shot is an acceptable and effective substitute, but International Shooting Sports Federation (ISSF) rules prevent its adoption. The present policy and rules of the ISSF on lead shot use contravene the International Olympic Committee (IOC) Charter position on environmental protection. The United Nations Environment Programme (UNEP), a formal Olympic partner on environmental protection, has no stated policy on contamination from lead ammunition, despite having declared lead a Priority Area for remedial action, and is pressing to remove lead from the global human environment. The IOC Sport and Environment Commission and UNEP could examine the continued use of lead shot ammunition and advise the IOC Executive Board on appropriate changes in policy and rules that could halt the massive lead shot contamination of shooting range environments world-wide.     

Glucosinolates in collard greens grown under three soil management practices

Glucosinolates (GSLs, β-D-thioglucoside-N-hydroxysulfates) are polar compounds present in varying amounts in members of the Brassicaceae family. They suppress soil-borne pests due to the biofumigant properties of the highly toxic isothiocyanates present in Brassica vegetables. The objectives of this investigation were to: (1) assess variation in GSLs concentrations among collard plants grown under three soil management practices: sewage sludge (SS) mixed with native soil, chicken manure (CM) mixed with native soil, and no-mulch (NM) native soil, (2) quantify GSLs concentrations in collard roots, leaves, and stems at harvest for potential use of their crude extracts in plant protection, and (3) assess myrosinase activity in soil amended with CM and SS mixed with native soil. Separation of GSLs was accomplished by adsorption on a DEAE-Sephadex ion exchange resin using disposable pipette tips filled with DEAE, a weak base, with a net positive charge when ionized and exchange anions such as GSLs (hydrophilic plant secondary metabolites). Quantification of total GSLs was based on inactivation of collard endogenous myrosinase and liberation of the glucose moiety from the GSLs molecule by addition of standardized myrosinase and colorimetric determination of the liberated glucose moiety. Across all treatments, SS and CM increased soil organic matter content from 2.2% in native soil to 4.2 and 6.5%, respectively. GSLs concentrations were significantly greater in collard leaves (30.9 µmoles g^?1 fresh weight) compared to roots and stems (7.8 and 1.2 µmoles g^?1 fresh weight), respectively. Leaves of collard grown in soil amended with SS contained the greatest concentrations of GSLs compared to leaves of plants grown in CM and NM treatments. Accordingly, leaves of collard plants grown in soil amended with SS could play a significant role in sustainable agriculture as alternative tools for soil-borne disease management in conventional and organic agriculture.     

Repellency and oviposition deterrence of wild tomato leaf extracts to spider mites,Tetranychus urticae Koch

Glandular trichomes on the leaves of wild tomato, Lycopersicon hirsutum f. hirsutum Mull, also known as Solanum habrochaites (Solanaceae) synthesize and accumulate high levels of methyl ketones (MKs). The potential of using MKs as alternatives to synthetic acaricides for controlling the twospotted spider mite, Tetranychus urticae Koch, is explored in this study. Plants of L. hirsutum accession LA 407 having high concentrations of MKs were grown from seeds under greenhouse conditions. The main objective of this investigation was to conduct bioassays that are quick and easy to implement, consistent over time (repeatable) with the ability to utilize small amounts of test material for testing repellency and fecundity (number of eggs laid by a female mite) of MKs in pure forms and in LA 407 crude extracts. Four MKs (2-tridecanone, 2-undecanone, 2-dodecanone, 2-pentadecanone) and their mixture were screened for their repellency and ability to alter fecundity of spider mites. All MKs repelled spider mites at the two periods tested. Following spraying of tomato leaf extracts prepared in ethanol (ethanol extracts), average number of eggs laid per female mite on bean leaf discs dropped from 0.8 to 0.3 and from 0.9 to 0.3 at 4 and 24 h after exposure representing 65 and 68% reduction, respectively. However, spraying of tomato leaf extracts prepared in water (water extracts) reduced number of eggs laid per female mite from 1.7 to 0.7 and from 2.6 to 0.9 at 4 and 24 h after exposure representing 60 and 67% reduction, respectively. We concluded that all MKs have repellent and egg laying deterrence activities against spider mites. This investigation suggests that ethanol and water extracts of LA 407 have a potential for repelling female spider mites and reducing their laid eggs which might be explored under field conditions for managing populations of spider mites, which could reduce reliance on synthetic acaricides.     

Kinetics of the oxidation of sucralose and related carbohydrates by ferrate(VI)

The kinetics of the oxidation of sucralose, an emerging contaminant, and related monosaccharides and disaccharides by ferrate(VI) (Fe(VI)) were studied as a function of pH (6.5-10.1) at 25°C. Reducing sugars (glucose, fructose, and maltose) reacted faster with Fe(VI) than did the non-reducing sugar sucrose or its chlorinated derivative, sucralose. Second-order rate constants of the reactions of Fe(VI) with sucralose and disaccharides decreased with an increase in pH. The pH dependence was modeled by considering the reactivity of species of Fe(VI), (HFeO(4)(-) and FeO(4)(2-)) with the studied substrates. Second-order rate constants for the reaction of Fe(VI) with monosaccharides displayed an unusual variation with pH and were explained by considering the involvement of hydroxide in catalyzing the ring opening of the cyclic form of the carbohydrate at increased pH. The rate constants for the reactions of carbohydrates with Fe(VI) were compared with those for other oxidant species used in water treatment and were briefly discussed.     

On-farm bioremediation of dimethazone and trifluralin residues in runoff water from an agricultural field

Bioremediation is the use of living organisms, primarily microorganisms, to degrade environmental contaminants into less toxic forms. Nine biobeds (ground cavity filled with a mixture of composted organic matter, topsoil, and a surface grass) were established at Kentucky State University research farm (Franklin County, KY) to study the impact of this practice on reducing surface runoff water contamination by residues of dimethazone and trifluralin herbicides arising from an agricultural field. Biobed (biofilter) systems were installed at the bottom of the slope of specially designed runoff plots to examine herbicides retention and degradation before entering streams and rivers. In addition to biobed systems, three soil management practices: municipal sewage sludge (SS), SS mixed with yard waste compost (SS + YW), and no-mulch rototilled bare soil (NM used for comparison purposes) were used to monitor the impact of soil amendments on herbicide residues in soil following natural rainfall events. Organic amendments increased soil organic matter content and herbicide residues retained in soil following rainfall events. Biobeds installed in NM soil reduced dimethazone and trifluralin by 84 and 82%, respectively in runoff water that would have been transported down the land slope of agricultural fields and contaminated natural water resources. Biobeds installed in SS and SS+YW treatments reduced dimethazone by 65 and 46% and trifluralin by 52 and 79%, respectively. These findings indicated that biobeds are effective for treating dimethazone and trifluralin residues in runoff water.     

Dissipation, half-lives, and mass spectrometric identification of endosulfan isomers and the sulfate metabolite on three field-grown vegetables

Endosulfan 3 EC, a mixture of α- and β-stereo isomers, was sprayed on field-grown pepper, melon, and sweet potato plants at the recommended rate of 0.44 kg A.I. acre(-1). Plant tissue samples (leaves, fruits, or edible roots) were collected 1 h to 30 days following spraying and analyzed for endosulfan isomers (α- and β-isomers). Analysis of samples was accomplished using a gas chromatograph (GC) equipped with a mass detector in total ion mode. The results indicated the formation of endosulfan sulfate as the major metabolite of endosulfan sulfite and the relatively higher persistence of the β-isomers as compared to the α-isomer. The initial total residues (α- and β-isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper and melon fruits, the α-isomer, which is the more toxic to mammals, dissipated faster (T(1/2) = 1.22 and 0.95 d, respectively) than the less toxic β-isomer (T(1/2) = 3.0 and 2.5 d, respectively). These results confirm the greater loss of the α-isomer compared to the β-isomer, which can ultimately impact endosulfan dissipation in the environment. Additionally, the higher initial residues of endosulfan on pepper and sweet potato leaves should be considered of great importance for timing field operations and the safe entry of harvesters due to the high mammalian toxicity of endosulfan.     

Liver lesions in demersal fishes near a large ocean outfall on the San Pedro Shelf, California

The prevalence of toxicopathic liver lesions in demersal fish on the San Pedro Shelf, California was determined for a 15-year period (1988–2003). Fish livers were sampled at fixed locations as part of the Orange County Sanitation Districts (OCSD) ocean monitoring program. Histopathological examination of selected fish liver tissues was studied to determine whether the wastewater discharge had affected fish health. The prevalence of toxicopathic lesion classes neoplasms (NEO), preneoplastic foci of cellular alteration (FCA), and hydropic vacuolation (HYDVAC) varied among species and locations. For all species sampled, severe lesions occurred in 6.2% of the fish examined (n = 7,694). HYDVAC (4.1%) was the most common toxicopathic lesion type followed by FCA (1.4%) and NEO (0.7%). HYDVAC occurred only in white croaker (Genyonemus lineatus), accounting for 84.8% of the toxicopathic lesions for this species. Prevalence of HYDVAC, NEO, and FCA in white croaker was 15.2, 2.0, and 0.7%, respectively. The prevalence of HYDVAC and NEO in white croaker increased with age and size but there was no sexual difference. A linear regression model was used for hypothesis testing to account for significant differences in fish size (and age for croakers) at the different sampling locations. This analysis showed that for HYDVAC there was no spatial or location effect for lesion rate or size/age of onset. For NEO, the model predicted that white croaker near the wastewater outfall may acquire these lesions at a smaller size/younger age, and at a higher rate, than at other sites. However, this result may be biased due to the unequal size frequency distributions and the low prevalence of NEO in white croaker at the different sampling sites. Bigmouth sole (Hippoglossina stomata) had a prevalence of FCA and NEO of 1.3 and 0.35%, respectively, but the prevalence and distribution of lesions was too few for statistical testing. There was no sexual difference for lesion prevalence in hornyhead turbot (Pleuronichthys verticalis) and the prevalence of FCA and NEO was 3.4 and 0.37%, respectively. FCA prevalence increased with size in hornyhead turbot and there were no significant spatial differences for lesion rates and fish size at lesion onset. Overall, consistent spatial differences for lesion prevalence were not demonstrated and highlight the analytical difficulties of detecting a possible point source impact when the effect is rare, correlated with the size/age structure of the population, and may be caused by exposure to unknown multiple sources. Thus, the usefulness of liver histopathology as a point-source monitoring tool is best applied to where the spatial scale of impact generally exceeds the home range of the target species.     

Thermal terrain modeling of spatial objects, a tool for environmental and climatic change assessment

The aim of the current research effort is to include biophysical multi-temporal data and more specifically land surface temperature (LST) in the terrain modeling process that traditionally was based only on digital elevation data processing. The terrain partition framework (spatial objects) is defined by the borderlines of prefecture authorities of Greece. Each object is represented by a set of attributes derived from the digital elevation data, and objects are organized into clusters on the basis of their terrain dependent representation. Finally, the terrain is segmented to regions on the basis of the multi-temporal LST data, each region presenting a different thermal signature. The thermal regions are used in the spatial objects parametric representation and a new index is devised (LST climatic index) expressing the biophysical suitability of spatial objects at moderate resolution scale.     

Trace metal dynamics in fishes from the southwest coast of India

The concentration of Fe, Co, Ni, Cu, Zn, Cd, and Pb in the muscle tissue of marine fishes like Lates calcarifer, Nemipterus japonicus, Caranx melampygus, Rastrelliger kanagurta, and Cyanoglossus macrostomus was estimated from samples collected in the continental shelf waters off Kochi and Mangalore on southwest coast of India. Species-specific and spatially heterogeneous patterns of tissue metals loads were apparent within the pelagic and demersal fish species for the two regions. The concentration ranges of Fe (541.60 to 649.60 ppm), Ni (12.12 to 13.92 ppm), and Cu (3.09 to 3.62 ppm) were higher in the demersal species C. melampygus, whereas Co (9.10 to 11.80 ppm) and Zn (79.30 to 84.30 ppm) were higher in the pelagic species L. calcarifer and Cd (4.35 to 6.38 ppm) were higher in the demersal species N. japonicus, possibly due to enhanced bioavailability of these metals from ecological processes associated with upwelling during the summer monsoon. The fish species showed a great capacity to accumulate metals, with highest bioaccumulation for the essential element iron and lowest bioaccumulation for the non-essential element lead. Among the demersal species, C. melampygus and N. japonicus had high concentration factors for the metals Fe (280,268 to 322,808), Ni (88,252 to 96,891), Cu (2,351 to 2,600), and Cd (29,637 to 32,404). In contrast, the pelagic species L. calcarifer and R. kanagurta had high concentration factors for the metals Zn (40,812 to 46,892), Co (280,285 to 423,037), and Pb (854 to 1,404).