Environmental fate of chlorothalonil in a Costa Rican banana plantation

The environmental fate of chlorothalonil (CHT) and its metabolites were studied under field-variable conditions in a commercial banana plantation in Costa Rica. Weather conditions were representative of a tropical environment and the fungicide applications were typical of those in banana production. The test plots were treated with Bravo 720 at 1.2 l ha(-1) of formulated product. Field persistence of CHT in soil and on banana leaves was measured during five consecutive months and after three aerial applications of the fungicide. Residues were analyzed in soil, sediment, water, banana leaves and drift cards by gas and liquid chromatography coupled to mass spectrometry. In soil and on the surface of banana leaves, CHT dissipated rapidly with half-lives of 2.2 and 3.9 d, respectively. Soil residues persisted and were detected 85 d after application. The main metabolite found in soil, 4-hydroxy-chlorothalonil, accounted for approximately 65% of residues detected and was measured up to 6d after application.     

Novel low density granular adsorbents - properties of a composite matrix from zeolitisation of vermiculite

This paper reports the preparation and properties of a new low density granular absorbent material based on a zeolite/vermiculite composite. The composite prepared addresses a number of important issues relating to the use of zeolites in environmental and waste management applications. The material prepared has large particle size due to binderless adhesion of zeolite crystals within the protective lamellar matrix provided by the vermiculite granule. Additionally, the porous nature of new material ensures that it outperforms natural zeolite grains in ion-exchange tests. The material was shown to have a low bulk density (0.75 g cm(-3)) adding the benefit that the majority of grains float on water for over 15 h. The conclusion of the study is that the use of composite matrices enable the preparation of materials which show the physical properties of the host, (e.g., granular and low density), whilst maintaining the powder-like properties (e.g., high ion-exchange and small crystal size) of the active component. The resulting material can be easily handled and separated from aqueous waste streams using either flotation or exploiting its granular nature.     

Effects of pH, organic acids, and competitive cations on mercury desorption in soils

The effects of pH, organic acids, and competitive cations on Hg(2+) desorption were studied. Three representative soils for rice production in China, locally referred to as a yellowish red soil (YRS), purplish clayey soil (PCS), and silty loam soil (SLS) and classified as Gleyi-Stagnic Anthrosols in FAO/UNESCO nomenclature, were, respectively, collected from Jiaxin County, Deqing County, and Xiasha District of Hangzhou City, Zhejiang Province. Most of the added Hg(2+) was adsorbed at low initial concentrations (<2 mg l(-1)). Desorption of the adsorbed Hg(2+) in 0.01M KCl (simulating soil solution) was minimal, but was significantly enhanced by the change of pH, and the presence of organic acids or competitive cations. The desorption of Hg(2+) in the soils decreased with pH from 3.0 to 5.0, leveled off at pH 5.0-8.0, but increased with pH from 7.0 to 9.0. The presence of organic ligands enhanced Hg(2+) desorption in the soils except for YRS, in which the addition of tartaric, malic, or oxalic acid reduced Hg(2+) desorption at low concentrations (<10(-4)M), but Hg(2+) desorption generally increased with organic acid concentration. Citric acid was most effective in increasing Hg(2+) desorption, followed by tartaric acid and malic acid; and oxalic acid was the least effective. Desorption of adsorbed Hg(2+) increased with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Hg(2+) desorption more than Zn(2+) at the same loading rate. CAPSULE: The effects of organic acids and competitive cations on Hg desorption in soil-water system are related to their concentrations, basic chemical properties, and soil properties.     

Risk of polycyclic aromatic hydrocarbon (PAH) exposure from ingested food: the Azerbaijan case study

Risks due to polycyclic aromatic hydrocarbons (PAHs) exposure from food consumption for the population of Azerbaijan were determined using deterministic and probabilistic methods. The guidelines and methods described and presented in the United States Environmental Protection Agency (U.S. EPA) Risk Assessment Guidance for Superfund (RAGS) Part A was used in performing the risk assessments. The current study utilized concentration data from different sources representing international studies performed over the past decade to determine those food products that contribute the most exposure to PAHs through ingestion for the Azeri population. Due to lack of concentration data from middle-Eastern countries, only European countries were considered and used for this analysis. Using the benzo[a]pyrene (BaP) toxicity equivalency factors (TEFs) to adjust the concentrations of the individual PAH compounds to BaP equivalent concentrations, risk analyses were performed. Deterministic risk estimates fell within probabilistic risk estimates. Child risks were consistently four to seven times higher in magnitude than adult risks. Risk potentials determined for the food exposure pathway were also determined to be up to ten times higher in magnitude than risks determined from exposures due to other pathways such as soil contamination. It was observed that three major factors contributed to the variability in the assessment results, which were child and adult body weights, consumption rates of the different food groups, and the variances of the input data. The most prevalent pathways of PAH exposure from the dietary patterns of the Azerbaijani population were determined to be from bread and bakery products, milk and dairy products, and egg products.     

Anaerobic degradation of nonylphenol in soil

This study investigated the effects of various factors on the anaerobic degradation of nonylphenol (NP) in soil. The results show that the optimal pH for NP degradation was 7.0 and that the degradation rate was enhanced when the temperature was increased. The addition of compost enhanced NP degradation. The individual addition of the electron donors lactate, acetate, and pyruvate inhibited NP degradation. The high-to-low order of NP degradation rates under three anaerobic conditions was sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The results show that sulfate-reducing bacteria, methanogen, and eubacteria are involved in the anaerobic degradation of NP, with sulfate-reducing bacteria being a major component of the soil. Of the anaerobic strains isolated from the soil samples, strain AT3 expressed the best ability to biodegrade NP.     

Contaminant exposure in terrestrial vertebrates

Here we review mechanisms and factors influencing contaminant exposure among terrestrial vertebrate wildlife. There exists a complex mixture of biotic and abiotic factors that dictate potential for contaminant exposure among terrestrial and semi-terrestrial vertebrates. Chemical fate and transport in the environment determine contaminant bioaccessibility. Species-specific natural history characteristics and behavioral traits then play significant roles in the likelihood that exposure pathways, from source to receptor, are complete. Detailed knowledge of natural history traits of receptors considered in conjunction with the knowledge of contaminant behavior and distribution on a site are critical when assessing and quantifying exposure. We review limitations in our understanding of elements of exposure and the unique aspects of exposure associated with terrestrial and semi-terrestrial taxa. We provide insight on taxa-specific traits that contribute, or limit exposure to, transport phenomenon that influence exposure throughout terrestrial systems, novel contaminants, bioavailability, exposure data analysis, and uncertainty associated with exposure in wildlife risk assessments. Lastly, we identify areas related to exposure among terrestrial and semi-terrestrial organisms that warrant additional research.     

Reduced nitrogen in ecology and the environment

Since the beginning of the 19th century humans have increasingly fixed atmospheric nitrogen as ammonia to be used as fertilizer. The fertilizers are necessary to create amino acids and carbohydrates in plants to feed animals and humans. The efficiency with which the fertilizers eventually reach humans is very small: 5-15%, with much of the remainder lost to the environment. The global industrial production of ammonia amounts to 117 Mton NH(3)-Nyear(-1) (for 2004). By comparison, we calculate that anthropogenic emissions of NH(3) to the atmosphere over the lifecycle of industrial NH(3) in agriculture are 45.3 Mton NH(3)-Nyear(-1), about half the industrial production. Once emitted ammonia has a central role in many environmental issues. We expect an increase in fertilizer use through increasing demands for food and biofuels as population increases. Therefore, management of ammonia or abatement is necessary.     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.     

Distribution and transport of coal tar-derived PAHs in fine-grained residuum

We investigated the distribution and transport of coal tar-derived polycyclic aromatic hydrocarbons (PAHs) in fine-grained residuum and alluvial floodplain deposits that underlie a former manufactured gas plant. All 16 USEPA priority pollutant PAHs are present at this site and have penetrated the entire 4-5m thickness of clayey sediments, which unconformably overly limestone bedrock. Concentrations of less hydrophobic PAHs (e.g., naphthalene, 0.011-384mg kg(-1)) were about 10 times higher than those of highly hydrophobic PAHs (e.g., benzo[g,h,i]perylene -0.002 to 56.03mgkg(-1)). Microscopic examination of thin-sections of the clay-rich sediments showed that fractures and rootholes, which can act as pathways for flow, occur throughout the profiles. Tarry residue was found coating some fractures and rootholes, indicating that coal tar was, in some cases, able to penetrate as an immiscible phase. However, in the vast majority of samples in which PAHs were detected, there was no detectable tar residue, suggesting that much of the transport occurred in the dissolved phase. Examination of thin-sections with an epifluorescent microscope indicated that PAHs, which fluoresce brightly when exposed to UV light, are distributed throughout the soil matrix, rather than being confined to fractures and rootholes. The widespread distribution of PAHs is most likely due to diffusion-controlled exchange between the fast-flow pathways in the fractures and rootholes and the relatively immobile water in the fine-grained matrix. This implies that fractures and rootholes can play a major role in controlling transport of highly hydrophobic compounds in fine-grained sediments, which would otherwise act as barriers to contaminant migration.     

Degradation of octylphenol and nonylphenol by ozone - part I: direct reaction

This aqueous reaction between ozone and two alkylphenols (APs), namely octylphenol (OP) and nonylphenol (NP), has been investigated. Both compounds are important endocrine disrupting chemicals, which arise from the biodegradation of alkylphenol ethoxylates and are often found at relatively high concentrations in wastewater effluents. In this paper the results of an experimental study are presented which provide values for the reaction rate constants between molecular ozone and undissociated OP and NP, and overall reaction rate constants for the degradation of the two APs at pH values in the range of 7-9. The kinetic rate constants for OP and NP degradation by molecular ozone were 4.33(+/-0.18) x 10(4) and 3.90(+/-0.10) x 10(4) M(-1) s(-1), and the reaction stoichiometry was similar in both cases and equal to approximately 1.3:1 ([O3]:[AP]). The overall second order reaction rate constants for the two APs increased significantly with increasing pH, which is believed to be mainly due to the increasing influence of indirect radical reaction with increasing pH; this aspect is considered in more detail in a companion paper. A preliminary investigation of the reaction mechanism suggests that an initial product of ozonation is hydroxyl-alkyl phenol.