Influence of Suspended Clay Minerals and Humic Matter on the Solid Phase Extraction Efficiency of Selected Pesticides from Water

The purpose of this investigation was to determine the influence of humic acids (HA) and Ca-montmorillonite (CaM) on the solid-phase extraction (SPE) efficiency of atrazine, alachlor and α-cypermethrin from water samples at various pH-values. The nature and intensity of binding of the studied pesticides to CaM were determined by X-ray diffraction analysis and termogravimetric analysis (TGA) test. The studied pesticides eluted from discs were analysed by thin-layer chromatography (TLC). The effects of CaM and humic acid were generally pH-dependent and acted independently in extraction efficiency influence. Lower recovery of pesticides was observed at higher pH values when CaM was ≥0.1 g and was attributed to greater dispersion of clay, increased surface area and subsequent adsorption. Concentrations of dissolved organic carbon (DOC) in humic acid had less effect on the extraction efficiency when water was at pH 8 compared to water at pH 2, which was probably due to greater nonpolar interactions of the pesticides to the charge-neutralized humic acid molecule.     

Reproductive and Physiological Effects of Environmental Contaminants in Fish-Eating Birds of the Great Lakes: A Review of Historical Trends

During the 1950s and 1960s, reproductive failures and population declines were observed in fish-eating birds such as gulls, terns, cormorants, herons, and eagles in the Great Lakes. DDE-induced eggshell thinning contributed to these declines, but other factors such as embryo toxicity also were implicated. With reduced releases of many pollutants, reproduction recovered in some species. However, biomonitoring during the 1980s and 1990s indicates continuing effects at highly contaminated sites. Improved analytical techniques and bioassays have allowed the assessment of the total dioxin-like toxicity of complex mixtures of organochlorines (TCDD-equivalents). Developmental defects such as embryo mortality, deformities, and edema have been associated with dioxin-like PCBs in several avian species. Improved biochemical techniques have allowed the measurement of biomarkers that detect physiological alterations associated with contaminants. Specific biomarkers studied in Great Lakes birds include cytochrome P-450 monooxygenases, highly carboxylated porphyrins, thyroxine, vitamin A, and immune function. Reproductive and physiological alterations are associated with population-level effects in Caspian terns and bald eagles that feed on highly contaminated fish. Biomonitoring using biomarkers and population-level measures in fish-eating birds will continue to be important for assessing the effects of contaminants on the Great Lakes ecosystem.     

Evidence of immunomodulation in nestling American kestrels (Falco sparverius) exposed to environmentally relevant PBDEs

We investigated whether exposure to environmentally relevant polybrominated diphenyl ethers (PBDEs) causes immunomodulation in captive nestling American kestrels (Falco sparverius). Eggs within each clutch, divided by laying sequence, were injected with safflower oil or penta-BDE congeners-47, -99, -100, and -153 dissolved in safflower oil (18.7 microg sigmaPBDEs/egg) approximating Great Lakes birds. For 29 days, nestlings consumed the same PBDE mixture (15.6+/-0.3 ng/g body weight per day), reaching sigmaPBDE body burden concentrations that were 120x higher in the treatment birds (86.1+/-29.1 ng/g ww) than controls (0.73+/-0.5 ng/g ww). PBDE-exposed birds had a greater PHA response (T-cell-mediated immunity), which was negatively associated with increasing BDE-47 concentrations, but a reduced antibody-mediated response that was positively associated with increasing BDE-183 concentrations. There were also structural changes in the spleen (fewer germinal centers), bursa (reduced apoptosis) and thymus (increased macrophages), and negative associations between the spleen somatic index and sigmaPBDEs, and the bursa somatic index and BDE-47. Immunomodulation from PBDE exposure may be exacerbated in wild birds experiencing greater environmental stresses.     

Data-directed modelling of Daphnia dynamics in a long-term micro-ecosystem experiment

The micro-ecosystem under consideration consists of three compartments forming a closed chain in which water circulates. Three trophic levels are represented in different compartments: autotrophs (algae, mainly Chlorella vulgaris), herbivores (Daphnia magna) and microbial decomposers. From a 20 years experiment with this system, data has been selected for this study. The dynamics of algae and Daphnia magna in only one of the compartments were modeled by different systems of differential and difference equations. We describe the successive steps in the process of model development, and the fitting of parameters using a Nelder-Mead simplex calibration method. Identification problems were overcome by taking values for physiological parameters in agreement with the literature. It turned out that a logistic type of model gives the best result for the structured Daphnia population because of the set up of the experiment: algae grow and reproduce in the upstream compartment. For this reason well-known plant–herbivore models did not comply with the data. The results of the parameter estimation procedure are discussed. The estimated grazing rate by Daphnia was smaller than expected. Possibly the Daphnia fed also on detritus and decomposing algae which were not measured.     

Contagious cooperation,temptation, and ecosystem collapse

Real world observations suggest that social norms of cooperation can be effective in overcoming social dilemmas such as the joint management of a common pool resource—but also that they can be subject to slow erosion and sudden collapse. We show that these patterns of erosion and collapse emerge endogenously in a model of a closed community harvesting a renewable natural resource in which individual agents face the temptation to overexploit the resource, while a cooperative harvesting norm spreads through the community via interpersonal relations. We analyze under what circumstances small changes in key parameters (including the size of the community, and the rate of technological progress) trigger catastrophic transitions from relatively high levels of cooperation to widespread norm violation—causing the social–ecological system to collapse.     

Monitoring the Elimination of Persistent Toxic Substances from the Great Lakes; Chemical and Physiological Evidence from Adult Herring Gulls

To assess progress towards virtual elimination of PCBs, DDE, dieldrin and Mirex and their associated physiological effects, we compared their concentrations in pooled livers of adult herring gulls (Larus argentatus) repeatedly sampled at 8 Great Lakes colonies and a reference colony on the Atlantic coast between 1974 and 1993. We measured the relative thyroid mass and concentrations of highly carboxylated porphyrins and retinyl palmitate in the liver of each individual. PCBs, dieldrin and mirex declined in 7 of 8 colonies while DDE decreased in six. The greatest decreases occurred pre-1985. PCBs and DDE did not decrease in gulls from Middle Island in western L. Erie. Middle Island and Saginaw Bay had the highest concentrations of PCBs of 11 Great Lakes colonies in the 1990s. Thyroids of gulls from Great Lakes colonies were slightly enlarged but the degree of enlargement has decreased over time. In 1991, gulls from Great Lakes colonies had slight to moderately elevated concentrations of highly carboxylated porphyrins. In the early 1990s, hepatic stores of retinyl palmitate were very seriously depleted in gulls from the Detroit River, western basin of Lake Erie, and Lake Ontario, reflecting decreased availability and altered storage. We conclude that PCBs and/or other persistent toxic substances in the food of herring gulls have not been virtually eliminated.