Acute and chronic ecotoxicity of carbaryl with a battery of aquatic bioassays

The ecotoxic effects of carbaryl (carbamate insecticide) were investigated with a battery of four aquatic bioassays. The nominal effective concentrations immobilizing 50% of Daphnia magna (EC50) after 24 and 48 h were 12.76 and 7.47 µg L^?1, respectively. After 21 days of exposure of D. magna, LOECs (lowest observed effect concentrations) for cumulative molts and the number of neonates per surviving adult were observed at carbaryl concentration of 0.4 µg L^?1. An increase of embryo deformities (curved or unextended shell spines) was observed at 1.8 and 3.7 µg L^?1, revealing that carbaryl could act as an endocrine disruptor in D. magna. Other bioassays of the tested battery were less sensitive: the IC50-72h and IC10-72h of the algae Pseudokirchneriella subcapitata were 5.96 and 2.87 mg L^?1, respectively. The LC50-6d of the ostracod Heterocypris incongruens was 4.84 mg L^?1. A growth inhibition of H. incongruens was registered after carbaryl exposure and the IC20-6d was 1.29 mg L^?1. Our results suggest that the daphnid test sensitivity was better than other used tests. Moreover, carbaryl has harmful and toxic effects on tested species because it acts at low concentrations on diverse life history traits of species and induce embryo deformities in crustaceans.     

Acid generation upon thermal concentration of natural water: The critical water content and the effects of ionic composition

Thermal evaporation of a variety of simulated pore waters from the region of Yucca Mountain, Nevada, produced acidic liquids and gases during the final stages of evaporation. Several simulated pore waters were prepared and then thermally distilled in order to collect and analyze fractions of the evolved vapor. In some cases, distillates collected towards the end of the distillation were highly acidic; in other cases the pH of the distillate remained comparatively unchanged during the course of the distillation. The results suggest that the pH values of the later fractions are determined by the initial composition of the water. Acid production stems from the hydrolysis of magnesium ions, especially at near dryness. Near the end of the distillation, magnesium nitrate and magnesium chloride begin to lose water of hydration, greatly accelerating their thermal decomposition to form acid. Acid formation is promoted further when precipitated calcium carbonate is removed. Specifically, calcium chloride-rich pore waters containing moderate (10–20 ppm) levels of magnesium and nitrate and low levels of bicarbonate produced mixtures of nitric and hydrochloric acid, resulting in a precipitous drop in pH to values of 1 or lower after about 95% of the original volume was distilled. Waters with either low or moderate magnesium content coupled with high levels of bicarbonate produced slightly basic fractions (pH 7–9). If calcium was present in excess of bicarbonate, waters containing moderate levels of magnesium produced acid even in the presence of bicarbonate, due to the precipitation of calcium carbonate. Other salts such as halite and anhydrite promote the segregation of acidic vapors from residual basic solids. The concomitant release of wet acid gas has implications for the integrity of the alloys under consideration for containers at the Yucca Mountain nuclear waste repository. Condensed acid gases at very low pH, especially mixtures of nitric and hydrochloric acid, are capable of corroding even alloys, such as nickel-based Alloy 22, which are considered to be corrosion-resistant under milder conditions.     

Household behaviour and attitudes with respect to recycling food waste--experiences from focus groups

It is a challenge to reduce the ever-increasing flow of waste. In Norway the systems for recycling of organic waste, paper, glass, metals, etc. differ between municipalities, both with regard to organizational and to technological structures. Our hypothesis is that people's attitudes and behaviour may differ with different systems of waste management. People's behaviour and attitudes regarding (organic) waste recycling were investigated in two municipalities with differing technical and organisational systems. Data came from interviews with municipal employees, questionnaires, focus groups and multi-criteria mapping. People seem to be better informed and more positive about organic waste recycling in one of the municipalities (MH, which has recycling of organic waste) than in the other (MS, which has no such recycling). The two municipalities had similar sets of important criteria for waste management (price, environmental friendliness, easy solutions, information). Many participants stated that they had learned from the group process, though only a few reported changed preferences. The institutional context seems to be important for people's behaviour and attitudes towards waste management. This implies that people's recycling behaviour does not only depend on technical and organisational aspects, but also on institutions. These are important messages for policy makers. On an individual basis, the different systems in the two municipalities seem to affect people's stated attitudes. These differences diminish when they are in a common setting where process and dialogue stimulate new thoughts and encourage people to act more altruistically.     

Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

Concentrations of polybrominated diphenyl ethers (PBDEs) in matched samples of human milk,dust and indoor air

Polybrominated diphenyl ethers (PBDEs) are lipophilic, persistent pollutants found worldwide in environmental and human samples. Exposure pathways for PBDEs remain unclear but may include food, air and dust. The aim of this study was to conduct an integrated assessment of PBDE exposure and human body burden using 10 matched samples of human milk, indoor air and dust collected in 2007–2008 in Brisbane, Australia. In addition, temporal analysis was investigated comparing the results of the current study with PBDE concentrations in human milk collected in 2002–2003 from the same region.PBDEs were detected in all matrices and the median concentrations of BDEs -47 and -209 in human milk, air and dust were: 4.2 and 0.3 ng/g lipid; 25 and 7.8 pg/m³; and 56 and 291 ng/g dust, respectively. Significant correlations were observed between the concentrations of BDE-99 in air and human milk (r = 0.661, p = 0.038) and BDE-153 in dust and BDE-183 in human milk (r = 0.697, p = 0.025). These correlations do not suggest causal relationships — there is no hypothesis that can be offered to explain why BDE-153 in dust and BDE-183 in milk are correlated. The fact that so few correlations were found in the data could be a function of the small sample size, or because additional factors, such as sources of exposure not considered or measured in the study, might be important in explaining exposure to PBDEs. There was a slight decrease in PBDE concentrations from 2002–2003 to 2007–2008 but this may be due to sampling and analytical differences. Overall, average PBDE concentrations from these individual samples were similar to results from pooled human milk collected in Brisbane in 2002–2003 indicating that pooling may be an efficient, cost-effective strategy of assessing PBDE concentrations on a population basis.The results of this study were used to estimate an infant's daily PBDE intake via inhalation, dust ingestion and human milk consumption. Differences in PBDE intake of individual congeners from the different matrices were observed. Specifically, as the level of bromination increased, the contribution of PBDE intake decreased via human milk and increased via dust. As the impacts of the ban of the lower brominated (penta- and octa-BDE) products become evident, an increased use of the higher brominated deca-BDE product may result in dust making a greater contribution to infant exposure than it does currently.To better understand human body burden, further research is required into the sources and exposure pathways of PBDEs and metabolic differences influencing an individual's response to exposure. In addition, temporal trend analysis is necessary with continued monitoring of PBDEs in the human population as well as in the suggested exposure matrices of food, dust and air.     

The Effect of Masterbatch Addition on the Mechanical, Thermal, Optical and Surface Properties of Poly(lactic acid)

There has been considerable interest in the use of the biodegradable polymer poly(lactic acid) (PLA) as a replacement for petroleum derived polymers due to ease of processability and its high mechanical strength. Other material properties have however limited its wider application. These include its brittle properties, low impact strength and yellow tint. In an attempt to overcome these drawbacks, PLA was blended with four commercially available additives, commonly known as masterbatches. The effect of the addition of 1.5 wt% of the four masterbatches on the mechanical, thermal, optical and surface properties of the polymer was evaluated. All four masterbatches had a slight negative effect on the tensile strength of PLA (3–5% reduction). There was a four fold increase in impact resistance however with the addition of one of the masterbatches. Differential scanning calorimetry demonstrated that this increase corresponded to a decrease in the polymer crystallinity. However there was an associated increase in polymer haze with the addition of this masterbatch. The clarity of PLA was improved through the addition of an optical brightener masterbatch, but the impact resistance remained low. The glass transition and melting temperatures of PLA were not affected by the addition of the masterbatches, and no change was observed in surface energy. Some delay in PLA degradation, in a PBS degradation medium at 50 °C, was observed due to blending with these masterbatches.     

The Vegetation of Wet Meadows in Relation to Their Land-use

Wetland biomonitoring approaches are needed to determine when changes in response to stressors are occurring and to predict the consequences of proposed land-use changes. These approaches require an understanding of shifts in biota that occur in response to land-use, data that are lacking for most kinds of wetlands. Changes in floristic composition corresponding to land-use differences at multiple scales (site to 2500 m radius) were characterized for 40 wet meadows associated with prairie glacial marshes in Minnesota (U.S.A.). In general, guild was more useful than species composition for indicating land-use impacts. Site impacts (stormwater, cultivation) and landscape disturbance (agriculture and urbanization, combined), coincide with a reduction in native graminoid and herbaceous perennial abundance (e.g., Carex lasiocarpa, Calamagrostis canadensis, Spartina pectinata). This vegetation is replaced with annuals (e.g, Bidens cernua, Polygonum pensylvanicum) in recently cultivated sites or introduced perennials (e.g., Phalaris arundinacea, Typha angustifolia) and floating aquatics (lemnids) in stormwater impacted wetlands. Ditches also reduce native perennial importance and increase perennials, but only when they are in highly impacted landscapes.     

Selection and application of a rainbow trout toxicity testing procedure for screening Sacramento River Watershed, California samples

A number of procedures have been developed to assess toxic effects on the early life stages of salmonid fish. In this study 13 rainbow trout embryo development relatively short-term (7 to 90 day) procedures were reviewed. Three 7-day methods from the published literature and three modifications developed at AQUA-Science (A-S) were evaluated in the laboratory. Based on that evaluation, A-S methods were selected for screening surface water samples (A-S 1) collected in the Sacramento River watershed (California) and for conducting toxicity identification evaluations (TIE) to identify cause(s) of toxicity. Test control performance, test sensitivity, and reference toxicant response variability in the A-S 1 were superior to those in commonly used freshwater toxicity testing methods. The incidence of Sacramento River watershed samples resulting in a notable decrease in embryo development was very low. Of 260 samples screened only 16 (6%) resulted in statistically significant inhibition of embryo development. Of the 16 toxic samples, nine caused minimal (less than 20% abnormal development) and four marginal (less than 30%) toxicity. Samples collected from the agriculture-dominated Colusa Basin Drain and rangeland/forest-dominated Battle Creek on June 16, 2005 caused significant toxicity. TIE procedures indicated that cationic chemicals were the primary cause of toxicity. Metals analysis did not reveal concentrations sufficient to inhibit embryo development, so the most probable cause of toxicity in the two samples was cationic chemicals (perhaps surfactants?) or metals that were not included in the analytical screening.     

Trace element levels in adults from the west coast of Canada and associations with age, gender, diet, activities, and levels of other trace elements

The purpose of this study was to assess trace element levels in whole blood, serum and urine of 61 non-smoking adults living on the west coast of Canada and to determine their association with the following variables: age, gender, diet, participation in certain hobby and/or occupational activities, and levels of other trace elements. Participants or their spouses were employed as oyster growers and were originally recruited to study the absorption of cadmium from oyster consumption. Trace elements were measured using inductively-coupled plasma mass spectrometry. A telephone interview was used to assess participant's intake of selected foods and the amount of time they have spent on certain activities over the lifetime. Comparison of results to previous studies revealed that blood lead, blood mercury, serum nickel, serum selenium and urine molybdenum levels were generally higher in this study than have previously been measured, possibly due to higher consumption of seafood in this sample. Men had statistically higher levels of serum iron, blood lead, and serum selenium, while women had statistically higher levels of serum copper and blood manganese. Blood lead levels increased with age. Diet had a statistically significant association with several elements. Consumption of spinach, seaweed, organ meats, and shellfish tended to be positively correlated with trace element concentrations and consumption of various forms of potatoes tended to be negatively correlated. Several statistically significant correlations were also observed between trace elements.