As part of the Endis-Risks project, the current study describes the occurrence of the chlorotriazine pesticides atrazine, simazine and terbutylazine in water, sediment and suspended matter in the Scheldt estuary (B-Nl) from 2002 to 2005 (3 samplings a year, 8 sampling points). Atrazine was found at the highest concentrations, varying from 10 to 736 ng/l in water and from 5 up to 10 ng/g in suspended matter. Simazine and terbutylazine were detected at lower concentrations. Traces of the targeted pesticides were also detected in sediments, but these were below the limit of quantification. As part of an ecotoxicological assessment, we studied the potential effect of atrazine on molting of Neomysis integer (Crustacea:Mysidacea), a resident invertebrate of the Scheldt Estuary and a proposed test organism for the evaluation of endocrine disruption. Following chronic exposure (3 weeks), atrazine did not significantly affect mysid molting at environmentally relevant concentrations (up to 1 μg/l). The water of the Scheldt estuary and its associated suspended solids are contaminated with chlorotriazines at concentrations that do not affect mysid molting.

There have been growing concerns about the environmental impact of Cu applied in the catfish pond aquaculture. In this paper, sediments taken from three commercial catfish ponds were studied for content, leachability, bioaccessibility, and speciation of sediment-bound Cu. Results showed that the Cu was concentrated in the top 10 cm of the sediments and the peak Cu concentrations ranged from the background level to about 200 mg/kg. Toxicity characteristic leaching procedure showed only 1-8% of sediment Cu was leachable while bioaccessible Cu, evaluated by physiological based extraction test, accounted for up to 40-85% of total Cu. Due to the high redox potential in the surface sediments, acid-volatile sulfide was not a significant binding phase. The sequential extraction results showed that the residual phase (forms in lattices of primary and secondary minerals) was the major Cu fraction in the first two pond sediments but carbonate-bound, Fe/Mn oxide-bound and organically bound Cu, as well as the residual fraction, seemed equally important in the third pond. Careful disposal of the Cu-laden pond sediment is necessary.

Occurrence and fate of alkylphenols (APs), known endocrine disruptors, were investigated in a Great Lakes coastal wetland, Cootes Paradise, ON. The wetland, which receives discharges from a Wastewater Treatment Plant (WTP) and several Combined Sewer Overflows (CSOs), is an important spawning ground for fish and crucial habitat for other fauna. Elevated concentrations of nonylphenol ethoxylates (NPEs) and their degradation product nonylphenol (NP) were found in water and sediment samples near the sources. Since transfer of APs through the food chain is of concern, we compared their concentrations in invertebrates from clean and contaminated sites. The results reveal transfer of alkylphenolics from sediments to biota and their accumulation in the invertebrate tissue, particularly the highly hydrophobic 4-NP, whose concentrations ranged from 1.9 to 6.3 μg g-1. To our knowledge, this is the first study to evaluate AP concentrations in tissue of benthic invertebrates under real environmental conditions. Concentrations of alkylphenolic compounds in water, sediments and benthic invertebrates in a large coastal wetland and implications for trophic transfer.

Organophosphorus pesticides (OPs) are ubiquitous in the environment and are highly toxic to amphibians. They deactivate cholinesterase, resulting in neurological dysfunction. Most chemicals in this group require oxidative desulfuration to achieve their greatest cholinesterase-inhibiting potencies. Oxon derivatives are formed within liver cells but also by bacterial decay of parental pesticides. This study examines the toxicity of chlorpyrifos, malathion and diazinon and their oxons on the foothill yellow-legged frog (Rana boylii). R. boylii is exposed to agricultural pesticides in the California Central Valley. Median lethal concentrations of the parental forms during a 96 h exposure were 3.00 mg/L (24 h) for chlorpyrifos, 2.14 mg/L for malathion and 7.49 mg/L for diazinon. Corresponding oxons were 10 to 100 times more toxic than their parental forms. We conclude that environmental concentrations of these pesticides can be harmful to R. boylii populations. Laboratory tests on the toxicity of OP insecticides and their oxons suggest that they may be acutely lethal to amphibians at ecologically relevant concentrations.

The purpose of this study is to develop a mechanistic model to describe a conceptually new “flux-biological response” approach based on biotic ligand model (BLM) and Michaelis-Menten (M-M) kinetics to allow the linkage between valve closure behavior and sodium (Na) transport mechanism in freshwater clam Corbicula fluminea in response to waterborne copper (Cu). We test the proposed model against published data regarding Na uptake kinetics in rainbow trout and Na uptake profile in C. fluminea, confirming that the predictive model is robust. Here, we show that the predicted M-M maximum Cu internalization flux in C. fluminea is 0.369 μmol g-1 h-1 with a half-saturation affinity constant of 7.87 x 10-3 μM. Dynamics of Na uptake and valve closure daily rhythm driven by external Cu can also be predicted simultaneously. We suggest that this “Na transport-valve closure behavior” approach might provide the basis of a future design of biomonitoring tool. A new flux-biological response model can link valve closure and sodium transport mechanisms in freshwater clam in response to copper.

Berkheya coddii Roessler (Asteraceae) is a hyper-accumulator of nickel, which can be used in phytomining and phytoremediation. Chrysolina pardalina Fabricius (Chrysomelidae) is a phytophagous leaf beetle, which may be useful in controlling population levels of B. coddii after it has been introduced into a new habitat. The aim of this study was to investigate the response of C. pardalina to topical application of dimethoate. Data recorded included the activity of acetylcholinesterase (AChE), the concentration of glutathione (GSH), and the activity of selected enzymes connected with GSH metabolism. Assays were carried out several times during the first 24 h after exposure to dimethoate. At the dosages used in this study, dimethoate was not as toxic as expected. AChE activity was significantly decreased 14 and 24 h after application. GST activity was significantly decreased 24 h after application. GSTPx activity was significantly decreased 2, 14 and 24 h after application. GR activity was significantly increased 4 h after application. GSH concentration was significantly increased 24 h after application. Long-term exposure to high levels of nickel may have caused adaptive changes in the enzymes that enable C. pardalina to deal with other stressors, including organophosphate pesticides. Long-term exposure to high levels of nickel may have caused adaptive changes in the enzymes that enable Chrysolina pardalina to deal with other stressors, including organophosphate pesticides.

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. Both biotic and abiotic factors determine chemical exposure for terrestrial vertebrates.

Tropospheric ozone (O3) was first determined to be phytotoxic to grapes in southern California in the 1950s. Investigations followed that showed O3 to be the cause of foliar symptoms on tobacco and eastern white pine. In the 1960s, “X” disease of ponderosa pines within the San Bernardino Mountains was likewise determined to be due to O3. Nearly 50 years of research have followed. Foliar O3 symptoms have been verified under controlled chamber conditions. Studies have demonstrated negative growth effects on forest tree seedlings due to season-long O3 exposures, but due to complex interactions within forest stands, evidence of similar losses within mature tree canopies remains elusive. Investigations on tree growth, O3 flux, and stand productivity are being conducted along natural O3 gradients and in open-air exposure systems to better understand O3 effects on forest ecosystems. Given projected trends in demographics, economic output and climate, O3 impacts on US forests will continue and are likely to increase. Elevated tropospheric ozone remains an important phytotoxic air pollutant over large areas of US forests.

This review summarizes and discusses the current understanding of human exposure to cyanobacterial toxins in “seafood” collected from freshwater and coastal areas. The review consists of three parts: (a) the existing literature on concentrations of cyanobacterial toxins in seafood is reviewed, and the likelihood of bioaccumulation discussed; (b) we derive cyanotoxin doses likely to occur through seafood consumption and propose guideline values for seafood and compare these to guidelines for drinking water; and (c) we discuss means to assess, control or mitigate the risks of exposure to cyanotoxins through seafood consumption. This is discussed in the context of two specific procedures, the food specific HACCP-approach and the water-specific Water Safety Plan approach by the WHO. Risks of exposure to cyanotoxins in food are sometimes underestimated. Risk assessments should acknowledge this and investigate the partitioning of exposure between drinking-water and food, which may vary depending on local circumstances.

Background, Aim and Scope Numerous herbicides and xenobiotic organic pollutants are detoxified in plants to glutathione conjugates. Following this enzyme catalyzed reaction, xenobiotic GS-conjugates are thought to be compartmentalized in the vacuole of plant cells. In the present study, evidence is presented for long range transport of these conjugates in plants, rather than storage in the vacuole. To our knowledge this is the first report about the unidirectional long range transport of xenobiotic conjugates in plants and the exudation of a glutathione conjugate from the root tips. This could mean that plants possess an excretion system for unwanted compounds which give them similar advantages as animals. Materials and Methods: Barley plants (Hordeum vulgare L. cv. Cherie) were grown in Petri dishes soaked with tap water in the greenhouse. - Fluorescence Microscopy. Monobromo- and Monochlorobimane, two model xenobiotics that are conjugated rapidly in plant cells with glutathione, hereby forming fluorescent metabolites, were used as markers for our experiments. Their transport in the root could be followed sensitively with very good temporal and spatial resolution. Roots of barley seedlings were cut under water and the end at which xenobiotics were applied was fixed in an aperture with a thin latex foil and transferred into a drop of water on a cover slide. The cover slide was fixed in a measuring chamber on the stage of an inverse fluorescence microscope (Zeiss Axiovert 100). - Spectrometric enzyme assay. Glutathione S-transferase (GST) activity was determined in the protein extracts following established methods. Aliquots of the enzyme extract were incubated with 1-chloro-2,4-dinitrobenzene (CDNB), or monochlorobimane. Controls lacking enzyme or GSH were measured. - Pitman chamber experiments. Ten days old barley plants or detached roots were inserted into special incubation chambers, either complete with tips or decapitated, as well as 10 days old barley plants without root tips. Compartment A was filled with a transport medium and GSH conjugate or L-cysteine conjugate. Compartments B and C contained sugar free media. Samples were taken from the root tip containing compartment C and the amount of conjugate transported was determined spectro-photometrically. Results: The transport in roots is unidirectional towards the root tips and leads to exsudation of the conjugates at rates between 20 and 200 nmol min-1. The microscopic studies have been complemented by transport studies in small root chambers and spectroscopic quantification of dinitrobenzene-conjugates. The latter experiments confirm the microscopic studies. Furthermore it was shown that glutathione conjugates are transported at higher rates than cysteine conjugates, despite of their higher molecular weights. This observation points to the existence of glutathione specific carriers and a specific role of glutathione in the root. Discussion: It can be assumed that long distance transport of glutathione conjugates within the plant proceeds like GSH or amino acid transport in both, phloem and xylem. The high velocity of this translocation of the GS-X is indicative of an active transport. For free glutathione, a rapid transport-system is essential because an accumulation of GSH in the root tip inhibits further uptake of sulfur. Taking into account that all described MRP transporters and also the GSH plasmalemma ATPases have side activities for glutathione derivatives and conjugates, co-transport of these xenobiotic metabolites seems credible. - On the other hand, when GS-B was applied to the root tips from the outside, no significant uptake was observed. Thus it can be concluded that only those conjugates can be transported in the xylem which are formed inside the root apex. Having left the root once, there seems to be no return into the root vessels, probably because of a lack of inward directed transporters. Conclusions: Plants seem to possess the capability to store glutathione conjugates in the vacuole, but under certain conditions, these metabolites might also undergo long range transport, predominantly into the plant root. The transport seems dependent on specific carriers and is unidirectional, this means that xenobiotic conjugates from the rhizosphere are not taken up again. The exudation of xenobiotic metabolites offers an opportunity to avoid the accumulation of such compounds in the plant. Recommendations and Perspectives: The role of glutathione and glutathione related metabolites in the rhizosphere has not been studied in any detail, and only scattered data are available on interactions between the plant root and rhizosphere bacteria that encounter such conjugates. The final fate of these compounds in the root zone has also not been addressed so far. It will be interesting to study effects of the exuded metabolites on the biology of rhizosphere bacteria and fungi.