Quantifying nitrogen process rates in a constructed wetland using natural abundance stable isotope signatures and stable isotope amendment experiments

This study describes the spatial variability in nitrogen (N) transformation within a constructed wetland (CW) treating domestic effluent. Nitrogen cycling within the CW was driven by settlement and mineralization of particulate organic nitrogen and uptake of NO3-. The concentration of NO3- was found to decrease, as the delta15N-NO3- signature increased, as water flowed through the CW, allowing denitrification rates to be estimated on the basis of the degree of fractionation of delta15N-NO3-. Estimates of denitrification hinged on the determination of a net isotope effect (eta), which was influenced byprocesses that enrich or deplete 15NO3- (e.g., nitrification), as well as the rate constants associated with the different processes involved in denitrification (i.e., diffusion and enzyme activity). The influence of nitrification on eta was quantified; however, it remained unclear how eta varied due to variability in denitrification rate constants. A series of stable isotope amendment experiments was used to further constrain the value of eta and calculate rates of denitrification, and nitrification, within the wetland. The maximum calculated rate of denitrification was 956 +/- 187 micromol N m(-2) h(-1), and the maximum rate of nitrification was 182 +/- 28.9 micromol N m(-2) h(-1). Uptake of NO3- was quantitatively more important than denitrification throughoutthe wetland. Rates of N cycling varied spatially within thewetland, with denitrification dominating in the downstream deoxygenated region of the wetland. Studies that use fractionation of N to derive rate estimates must exercise caution when interpreting the net isotope effect. We suggest a sampling procedure for future natural abundance studies that may help improve the accuracy of N cycling rate estimates.     

The application of profluorescent nitroxides to detect reactive oxygen species derived from combustion-generated particulate matter: Cigarette smoke – A case study

Reactive oxygen species (ROS) and related free radicals are considered to be key factors underpinning the various adverse health effects associated with exposure to ambient particulate matter. Therefore, measurement of ROS is a crucial factor for assessing the potential toxicity of particles. In this work, a novel profluorescent nitroxide, BPEAnit, was investigated as a probe for detecting particle-derived ROS. BPEAnit has a very low fluorescence emission due to inherent quenching by the nitroxide group, but upon radical trapping or redox activity, a strong fluorescence is observed. BPEAnit was tested for detection of ROS present in mainstream and sidestream cigarette smoke. In the case of mainstream cigarette smoke, there was a linear increase in fluorescence intensity with an increasing number of cigarette puffs, equivalent to an average of 101 nmol ROS per cigarette based on the number of moles of the probe reacted. Sidestream cigarette smoke sampled from an environmental chamber exposed BPEAnit to much lower concentrations of particles, but still resulted in a clearly detectible increase in fluorescence intensity with sampling time. It was calculated that the amount of ROS was equivalent to 50 ± 2 nmol per mg of particulate matter; however, this value decreased with ageing of the particles in the chamber. Overall, BPEAnit was shown to provide a sensitive response related to the oxidative capacity of the particulate matter. These findings present a good basis for employing the new BPEAnit probe for the investigation of particle-related ROS generated from cigarette smoke as well as from other combustion sources.     

Phosmet residues in an orchard and adjacent recreational area 1

Abstract

Two cover sprays of phosmet were applied to an orchard adjoining a camping area and a bird sanctuary with a resident goose population. Insecticide residues were monitored on orchard leaves, orchard ground cover, ground cover in the camp‐site and along the adjacent lakeshore. Despite attempts to minimize drift, significant spray residues were found outside the target area. Residues on ground cover and leaves were reduced by sprinkler irrigation subsequent to spray application.     

Effects of agricultural pesticides on the health of Rana pipiens frogs sampled from the field

There is evidence that over the last 30 years, there have been mass declines in diverse geographic locations among amphibian populations due to disease outbreaks. Multiple causes have been suggested to explain this increase in disease incidence. Among these, climate changes, environmental pollution and reduced water quality are gaining attention. Indeed, some chemicals of environmental concerns are known to alter the immune system. It is possible that exposure to these pollutants could alter the immune system of anurans and render them more susceptible to different pathogens. In this study, we sampled Rana pipiens in five different sites near St. Lawrence River (Quebec, Canada) during the months of July and September in 2001. Two of these sites were protected areas, in which low levels of pesticides were detected, while the remaining three sites were located in areas with intensive corn and soybeans cultivations. Our results demonstrated that frogs living in agricultural regions are smaller in size and weight than frogs living in areas with lower levels of pesticides at both sampling times. Moreover, we have observed a significant decrease in the number of splenocytes (cellularity) and the phagocytic activity in frogs sampled in impacted sites. Taken together, these results suggest that frogs living in agricultural regions might be more vulnerable to infections and diseases through their smaller size and alteration of their immune system. Our results also contribute to the overall discussion on factors involved in amphibian declines.     

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM₁₀ and PM_2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO₂, PM₁₀, NO₂, CO, and O₃; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ng?m^?3, surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10^?6) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98?×?10^?7 in PM₁₀ and 1.06?×?10^?6 in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO₂, NO₂, PM₁₀, CO, and solar radiation had positive correlation with PAHs concentrations, while O₃, temperature, relative humidity, and wind speed were negatively correlated.     

Cadmium (Cd2+) removal by nano zerovalent iron: surface analysis, effects of solution chemistry and surface complexation modeling

Nano zerovalent iron (nZVI) is an effective remediant for removing various organic and inorganic pollutants from contaminated water sources. Batch experiments were conducted to characterize the nZVI surface and to investigate the effects of various solution properties such as pH, initial cadmium concentration, sorbent dosage, ionic strength, and competitive ions on cadmium removal by nZVI. Energy-dispersive X-ray and X-ray photoelectron spectroscopy results confirmed removal of Cd²⁺ ions by nZVI through adsorption. Cd²⁺ adsorption decreased in the presence of competitive cations in the order: Zn²⁺?>?Co²⁺?>?Mg²⁺?>?Mn²⁺?=?Cu²⁺?>?Ca²⁺?>?Na²⁺?=?K⁺. Higher concentrations of Cl^? significantly decreased the adsorption. Cadmium removal increased with solution pH and reached a maximum at pH 8.0. The effects of various solution properties indicated Cd²⁺ adsorption on nZVI to be a chemisorption (inner-sphere complexation) process. The three surface complexation models (diffuse layer model, constant capacitance model, and triple layer model) fitted well to the adsorption edge experimental data indicating the formation of nZVI–Cd bidentate inner-sphere surface complexes. Our results suggest that nZVI can be effectively used for the removal of cadmium from contaminated water sources with varying chemical conditions.     

Comparative acute toxicity of two phytosanitary molecules,lambda-cyhalothrin and acetamiprid,on Nile Tilapia (Oreochromis Niloticus) juveniles

Abstract

This study aimed to compare the toxicity for fish of two active ingredients (lambda-cyhalothrin-20?g L^?1, a pyrethroid, and acetamiprid-15?g L^?1, a neonicotinoid) which are components of a commercial insecticide (Acer 35 EC) used in cotton crop in many West African countries. The juveniles of Oreochromis niloticus (4.01?±?0.34?g, mean body weight) were exposed for 96?h to increasing concentrations of active ingredients (lambda-cyhalothrin and acetamiprid) or a mixture similar to Acer 35 EC (composed by 20?g of chemical compound lambda-cyhalothrin and 15?g of acetamiprid dissolved in 1?L of acetone). The experiments were carried out under controlled conditions in aquaria according to OECD Guidelines. During the experiments, the behavioral responses (loss of balance, color change, hyperactivity, etc.) that usually precede death were observed in exposed fish. Mortalities were recorded in each aquarium and the LC₅₀-96h of each chemical was determined. The LC₅₀-96h obtained were respectively 0.1268, 0.0029, 182.9 and 0.5685?ppm for Acer 35 EC, lambda-cyhalothrin, acetamiprid and mixture. All insecticides used in this study had profound impact on Nile tilapia behavior which may confirm the neurotoxicity of each single active compound as well as of their mixture.