Environmental distribution of PAHs in pine needles,soils, and sediments

Introduction  

The content of 16 polycyclic aromatic hydrocarbons (PAHs) was determined in 60 samples from three environmental matrices (soils, sediments, and pine needles) in an effort to assess their distribution on a river basin scale.     

Amazon River dissolved load: temporal dynamics and annual budget from the Andes to the ocean

The aim of the present study is to estimate the export fluxes of major dissolved species at the scale of the Amazon basin, to identify the main parameters controlling their spatial distribution and to identify the role of discharge variability in the variability of the total dissolved solid (TDS) flux through the hydrological cycle. Data are compiled from the monthly hydrochemistry and daily discharge database of the “Programa Climatologico y Hidrologico de la Cuenca Amazonica de Bolivia” (PHICAB) and the HYBAM observatories from 34 stations distributed over the Amazon basin (for the 1983–1992 and 2000–2012 periods, respectively). This paper consists of a first global observation of the fluxes and temporal dynamics of each geomorphological domain of the Amazon basin. Based on mean interannual monthly flux calculations, we estimated that the Amazon basin delivered approximately 272?×?10⁶ t year^?1 (263–278) of TDS during the 2003–2012 period, which represents approximately 7 % of the continental inputs to the oceans. This flux is mainly made up by HCO₃, Ca and SiO₂, reflecting the preferential contributions of carbonate and silicate chemical weathering to the Amazon River Basin. The main tributaries contributing to the TDS flux are the Marañon and Ucayali Rivers (approximately 50 % of the TDS production over 14 % of the Amazon basin area) due to the weathering of carbonates and evaporites drained by their Andean tributaries. An Andes–sedimentary area–shield TDS flux (and specific flux) gradient is observed throughout the basin and is first explained by the TDS concentration contrast between these domains, rather than variability in runoff. This observation highlights that, under tropical context, the weathering flux repartition is primarily controlled by the geomorphological/geological setting and confirms that sedimentary areas are currently active in terms of the production of dissolved load. The log relationships of concentration vs discharge have been characterized over all the studied stations and for all elements. The analysis of the slope of the relationship within the selected contexts reveals that the variability in TDS flux is mainly controlled by the discharge variability throughout the hydrological year. At the outlet of the basin, a clockwise hysteresis is observed for TDS concentration and is mainly controlled by Ca and HCO₃ hysteresis, highlighting the need for a sampling strategy with a monthly frequency to accurately determine the TDS fluxes of the basin. The evaporite dissolution flux tends to be constant, whereas dissolved load fluxes released from other sources (silicate weathering, carbonate weathering, biological and/or atmospheric inputs) are mainly driven by variability in discharge. These results suggest that past and further climate variability had or will have a direct impact on the variability of dissolved fluxes in the Amazon. Further studies need to be performed to better understand the processes controlling the dynamics of weathering fluxes and their applicability to present-day concentration–discharge relationships at longer timescales.     

Variation patterns in individual fish responses to chemical stress among estuaries, seasons and genders: the case of the European flounder (Platichthys flesus) in the Bay of Biscay

The objective was to describe and model variation patterns in individual fish responses to contaminants among estuaries, season and gender. Two hundred twenty-seven adult European flounders were collected in two seasons (winter and summer) in four estuaries along the Bay of Biscay (South West France), focusing on a pristine system (the Ster), vs. three estuaries displaying contrasted levels of contaminants (the Vilaine, Loire and Gironde). Twenty-three variables were measured by fish, considering the load of contaminants (liver metals, liver and muscle persistent organic pollutants, muscle polycyclic aromatic hydrocarbons); the gene expression (Cyt C oxydase, ATPase, BHMT, Cyt P450 1A1, ferritin); the blood genotoxicity (Comet test); and liver histology (foci of cellular alteration–tumour, steatosis, inflammation, abnormal glycogen storage). Canonical redundancy analysis (RDA) was used to model these variables using gender, season and estuary of origin as explanatory variables. The results underlined the homogeneity of fish responses within the pristine site (Ster) and more important seasonal variability within the three contaminated systems. The complete model RDA was significant and explained 35 % of total variance. Estuary and season respectively explained 30 and 5 % of the total independent variation components, whilst gender was not a significant factor. The first axis of the RDA explains nearly 27 % of the total variance and mostly represents a gradient of contamination. The links between the load of contaminants, the expression of several genes and the biomarkers were analysed considering different levels of chemical stress and a possible multi-stress, particularly in the Vilaine estuary.     

Thermodynamic and kinetic study of phenol degradation by a non-catalytic wet air oxidation process

This work is dedicated to an accurate evaluation of thermodynamic and kinetics aspects of phenol degradation using wet air oxidation process. Phenol is a well known polluting molecule and therefore it is important having data of its behaviour during this process. A view cell is used for the experimental study, with an internal volume of 150 mL, able to reach pressures up to 30 MPa and temperatures up to 350 °C. Concerning the thermodynamic phase equilibria, experimental and modelling results are obtained for different binary systems (water/nitrogen, water/air) and ternary system (water/nitrogen/phenol). The best model is the Predictive Soave Redlich Kwong one. This information is necessary to predict the composition of the gas phase during the process. It is also important for an implementation in a process simulation. The second part is dedicated to kinetics evaluation of the degradation of phenol. Different compounds have been detected using GC coupled with a MS. A kinetic scheme is deduced, taking into account the evolution of phenol, hydroquinones, catechol, resorcinol and acetic acid. The kinetic parameters are calculated for this scheme. These data are important to evaluate the evolution of the concentration of the different polluting molecules during the process. A simplified kinetic scheme, which can be easily implemented in a process simulation, is also determined for the direct degradation of phenol into H₂O and CO₂. The Arrhenius law data obtained for the phenol disappearance are the following: k = 1.8 × 10⁶ ± 3.9 × 10⁵ M⁻¹ s⁻¹ (pre-exponential factor) and E_a = 77 ± 8 kJ mol⁻¹ (activation energy).     

Realistic approach of pesticide residues and French consumer exposure within fruit & vegetable intake

The increase of fruit and vegetable (F&V) intake contributes to the prevention of chronic diseases, but could also significantly increase pesticide exposure and may thus be of health concern. Following a previous pesticide exposure assessment study, the present study was carried out to determine actual levels of pesticides within 400 g of F&V intake and to evaluate consumer risk. Forty-three Active Substances (AS) exceeding 10 % of the Acceptable Daily Intake (ADI) in balanced menus established for our previous theoretical study were considered. Fifty-six pooled food samples were analyzed: 28 fruit samples and 28 vegetable samples. Pesticide values were compared to Maximum Residue Levels (MRL) and to the "toxicological credit" derived from ADI. It was observed that 23 out of the 43 retained AS were never detected, 5 were detected both in F&V samples, 12 only in fruits and 3 only in vegetables. The most frequently detected AS were carbendazim, iprodione and dithiocarbamates. When detected, AS were more frequently found in fruit samples (74 %) than in vegetable samples (26 %). A maximum of 3 AS were detected at once in a given sample. Overall, we observed 8 and 14 overruns of the MRL in 1204 measures in pooled vegetable and fruit samples, respectively (0.7 % and 1.2 % of cases, respectively). Chronic exposure for adults was the highest for dithiocarbamates but did not exceed 23.7 % of the ADI in F&V. It was concluded that raising both F&V consumption up to 400 g/day (~5 F&V/day) according to recommendations of the national health and nutrition plan, does not induce pesticide overexposure and should not represent a risk for the consumer.     

An evaluation of the estimation of road traffic emission factors from tracer studies

Road traffic emission factors (EFs) are one of the main sources of uncertainties in emission inventories; it is necessary to develop methods to reduce these uncertainties to manage air quality more efficiently. Recently an alternative method has been proposed to estimate the EFs. In that work the emission factors were estimated from a long term tracer study developed in Ho Chi Minh City (HCMC) Vietnam. A passive tracer was continuously emitted from a finite line source placed in one side of an urban street canyon. Simultaneously, the resulting tracer concentrations were monitored at the other side of the street. The results of this experiment were used to calculate the dispersion factors and afterwards, these dispersion factors were used to estimate the EFs. In this paper we use the Computational Fluids Dynamics (CFD) model WinMISKAM to critically evaluate the proposed methodology.In a first step, we use the results of the tracer study to validate the CFD model. Results show that the model is able to simulate quite well the tracer dispersion in most of the cases. The model is then used to evaluate the effect of varying the source configuration and to correct the EFs. A comparison with available studies shows that the corrected EFs are within the range of the EFs reported in other studies. Finally, the CFD model is used to find a source configuration that better represents the vehicle emissions and that may be used in future studies to estimate the EFs more accurately. Results show that a 200 m line placed in the center of the street would represent very well the vehicle emissions. This work shows that it is possible to accurately estimate the EFs from tracer studies.     

A microcosm system to evaluate the toxicity of the triazine herbicide simazine on aquatic macrophytes

This study evaluates the effects of the triazine herbicide simazine in an outdoor pond microcosm test system that contained two submerged rooted species (Myriophyllum spicatum and Elodea canadensis) and two emergent rooted species (Persicaria amphibia and Glyceria maxima) over a period of 84 days. Simazine was applied to the microcosms at nominal concentrations of 0.05, 0.5 and 5 mg/L. General biological endpoints and physiological endpoints were used to evaluate herbicide toxicity on macrophytes and the algae developing naturally in the system.Concentration-related responses of macrophytes and algae were obtained for the endpoints selected, resulting in a no observed ecologically adverse effect concentration (NOEAEC) at simazine concentrations of 0.05 mg active ingredient/L after 84 days. E. canadensis was the most negatively affected species based on length increase, which was consistently a very sensitive parameter for all macrophytes. The experimental design presented might constitute a suitable alternative to conventional laboratory single-species testing.     

Spring-harvested game birds in the Western James Bay region of Northern Ontario, Canada: the amount of organochlorines in matched samples of breast muscle, skin, and abdominal fat

We examined matched-tissue samples (the right pectoral muscle plus the associated skin and fat was considered a breast portion) of 81 spring-harvested waterfowl and 19 summer-harvested godwits (Limosa spp.) to assess the potential of these water birds contributing to the body burden of PCBs and DDT noted in First Nation people of the western James Bay region, northern Ontario, Canada. In general, the dabbling ducks (mallard duck, Anas platyrhynchos; and northern pintail, A. acuta) had significantly lower percent lipid (gravimetrically determined) values in skin tissue, fat tissue, and breast muscle compared to the goose species (Canada goose, Branta canadensis; lesser snow goose, Chen caerulescens); godwits had percent lipid values not significantly different than ducks and geese. Also, the percent lipid values in skin for all species of birds examined approached those found in fat tissue. Organochlorine data were expressed as the amount (microg) of each contaminant per breast portion to show contaminant consumption in terms of typical and easily recognizable dietary portions; direct comparisons were made to acceptable daily intake (ADI) or tolerable daily intake (TDI) values as recommended by Health Canada. Significant differences in the amount of organochlorines between bird species for skin, fat tissue, and breast muscle samples were found. In general, breast portions from snow geese contained the least amount of organochlorines, followed by godwits (except for mirex) and then Canada geese; the dabbling ducks had the greatest amount of organochlorines on a breast portion basis. However, on average, no 60 kg person would exceed the calculated organochlorine ADI/TDI values consuming one breast portion (i.e., breast + associated skin and fat), but the maximum value of SigmaPCBs for skin tissue alone in male mallards (47 microg) was more than twice the ADI/TDI (18 microg/day); while, that in fat tissue alone (17 microg) approached the ADI/TDI. Thus, the consumption of dabbling ducks by children is an issue that should be explored further, if tissue other than breast muscle is eaten. Lastly, the consumption of waterfowl was a source of PCBs for people of Fort Albany and Kashechewan, but not DDT, as this organochlorine was infrequently detected.     

Water Conservation Versus Soil Salinity Control

This paper tackles the increasingly significant problem of irrigation-induced soil salinity within a groundwater management model. Irrigation can result not only in heavier salt concentrations but also in the removal of salt from the soil through return flows. Given these contradictory observations, we are interested in the effects on soil salt concentration if irrigation efficiency is improved. We develop a model of salt concentration patterns in both soil and groundwater. We introduce a negative externality to the production process by assuming that soil degradation due to higher soil salinity affects total factor productivity. Within this framework, we show that in the presence of this externality, increasing irrigation efficiency can lead to higher or lower soil salt concentration, depending on the social cost of transferring salt from one reservoir to another.