An integrated approach for assessing the migration behavior of chlorpyrifos and carbaryl in the unsaturated soil zone

Chlorpyrifos (O, O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) and carbaryl (1-naphthyl methylcarbamate) are often applied concurrently as insecticides in food production. The aim of this study was to research their migration behavior in a real environment. We researched the leaching of both pesticides by setting up field lysimeters on a farm with the typical soil used in fruit production today. In order to analyze the variables involved in this process, we performed complementary adsorption studies, we performed complementary adsorption studies using batches and undisturbed soil laboratory columns for both compounds. The results for pesticide transport through the lysimeters showed that less than 1% of chlorpyrifos was recovered in the leachates, while almost 17% was recovered for carbaryl. Having completed the experiment in undisturbed laboratory columns, soil analysis showed that chlorpyrifos mainly remained in the first 5 cm, while carbaryl moved down to the lower sections. These results can be explained in view of the sorption coefficient values (K_D) obtained in horizons A and B for chlorpyrifos (393 and 184 L kg^?1) and carbaryl (3.1 and 4.2 L kg^?1), respectively. By integrating the results obtained in the different approaches, we were able to characterize the percolation modes of these pesticides in the soil matrix, thus contributing to the sustainable use of resources.     

Development and implementation of eco-genomic tools for aquatic ecosystem biomonitoring: the SYNAQUA French-Swiss program

The effectiveness of environmental protection measures is based on the early identification and diagnosis of anthropogenic pressures. Similarly, restoration actions require precise monitoring of changes in the ecological quality of ecosystems, in order to highlight their effectiveness. Monitoring the ecological quality relies on bioindicators, which are organisms revealing the pressures exerted on the environment through the composition of their communities. Their implementation, based on the morphological identification of species, is expensive because it requires time and experts in taxonomy. Recent genomic tools should provide access to reliable and high-throughput environmental monitoring by directly inferring the composition of bioindicators’ communities from their DNA (metabarcoding). The French-Swiss program SYNAQUA (INTERREG France-Switzerland 2017–2019) proposes to use and validate the tools of environmental genomic for biomonitoring and aims ultimately at their implementation in the regulatory bio-surveillance. SYNAQUA will test the metabarcoding approach focusing on two bioindicators, diatoms, and aquatic oligochaetes, which are used in freshwater biomonitoring in France and Switzerland. To go towards the renewal of current biomonitoring practices, SYNAQUA will (1) bring together different actors: scientists, environmental managers, consulting firms, and biotechnological companies, (2) apply this approach on a large scale to demonstrate its relevance, (3) propose robust and reliable tools, and (4) raise public awareness and train the various actors likely to use these new tools. Biomonitoring approaches based on such environmental genomic tools should address the European need for reliable, higher-throughput monitoring to improve the protection of aquatic environments under multiple pressures, guide their restoration, and follow their evolution.     

Household water insecurity and its cultural dimensions: preliminary results from Newtok,Alaska

Using a relational approach, I examine several cultural dimensions involved in household water access and use in Newtok, Alaska. I describe the patterns that emerge around domestic water access and use, as well as the subjective lived experiences of water insecurity including risk perceptions, and the daily work and hydro-social relationships involved in accessing water from various sources. I found that Newtok residents haul water in limited amounts from a multitude of sources, both treated and untreated, throughout the year. Household water access is tied to hydro-social relationships predicated on sharing and reciprocity, particularly when the primary treated water access point is unavailable. Older boys and young men are primarily responsible for hauling water, and this role appears to be important to male Yupik identity. Many interviewees described preferring to drink untreated water, a practice that appears related to cultural constructions of natural water sources as pure and self-purifying, as well as concerns about the safety of treated water. Concerns related to the health consequences of low water access appear to differ by gender and age, with women and elders expressing greater concern than men. These preliminary results point to the importance of understanding the cultural dimensions involved in household water access and use. I argue that institutional responses to water insecurity need to incorporate such cultural dimensions into solutions aimed at increasing household access to and use of water.     

Photocatalytic reduction of carbon dioxide over Cu/TiO<Subscript>2</Subscript> photocatalysts

The photocatalytic reduction of CO₂ with H₂O was investigated using Cu/TiO₂ photocatalysts in aqueous solution. For this purpose, Cu/TiO₂ photocatalysts (with 0.2, 0.9, 2, 4, and 6 wt.% of Cu) have been synthesized via sol-gel method. The photocatalysts were extensively characterized by means of inductively coupled plasma optical emission spectrometry (ICP-OES), N₂ physisorption (BET), XRD, UV-vis DRS, FT-IR, Raman spectroscopy, TEM-EDX, and photoelectrochemical measurements. The as-prepared photocatalysts contain anatase as a major crystalline phase with a crystallite size around 13 nm. By increasing the amount of Cu, specific surface area and band gap energy decreased in addition to the formation of large agglomeration of CuO. Results revealed that the photocatalytic reduction of CO₂ decreased in the presence of Cu/TiO₂ in comparison to pure TiO₂, which might be associated to the formation of CuO phase acting as a recombination center of generated electron-hole pair. Decreasing of photoactivity can also be connected with a very low position of conduction band of photocatalysts with high Cu content, which makes H₂ production necessary for CO₂ reduction more difficult.     

Trace metal (Cd,Cu, Pb,Zn) fractionation in urban-industrial soils of Ust-Kamenogorsk (Oskemen), Kazakhstan—implications for the assessment of environmental quality

Ust-Kamenogorsk is one of the largest cities and industrial centers in Kazakhstan. Non-ferrous metallurgy (Zn–Pb smelter) has acted as a predominating industrial branch in the city since late 1940s. The industrial plants are situated directly adjacent to the residential area of the city which creates grievous ecotoxicological hazard. In the present paper, we aimed at assessing the trace metal pollution of top soils in Ust-Kamenogorsk and its potential threats to the local population. The top soils were sampled at 10 sites throughout the city center. We determined the physical and chemical properties of soils as well as the contents of Cd, Cu, Pb, and Zn. In addition, the soil samples were subjected to a five-step sequential extraction to ascertain the fractionation of trace metals. On this basis, we calculated the geoaccumulation index (I_geo) and pollution load index (PLI) and assessed bioavailability of the elements. From our data, it emerged that the soils displayed a strong polymetallic pollution. PLI was as high as 33.4. Throughout the city, the trace metal contents exceeded the geochemical background and allowable values for residential, recreational, and institutional areas. The I_geo obtained were 3.7–6.5 for Cd, 1.5–4.7 for Cu, 2.8–5.7 for Pb, and 2.6–4.6 for Zn. The soils in Ust-Kamenogorsk displayed extremely high contamination with Cd, moderate to strong contamination with Pb and Zn, and low to moderate contamination with Cu. Cd and Pb were found to be the most bioavailable elements. The mobility of trace metals in the soils changed in the order Cd > Pb > Zn > Cu.     

Water quality index for agricultural systems in Northwest Uruguay

Agricultural systems have experienced rapid expansion and intensification in the last several decades. In Uruguay, since the beginning of 2000, the most common cropping systems have included soybeans. Currently, this crop is expanding towards lowlands traditionally occupied by rice in rotation with pastures. However, the environmental effects of agricultural intensification and diversification are not well known. Thus, some indices have been proposed to quantify the changes in agricultural production systems and assess water quality. The main goal of this study was to develop a water quality index (WQI) to assess the impacts of the diversification of rice production systems in northwest Uruguay. The study was carried out in an agricultural basin where other summer crops have been incorporated in the rice-pasture sequence. Agriculture intensification and crop diversification indices were calculated using information provided by farmers. Water samples were collected downstream of the production area before crop sowing and after crop harvest (2008–2009 to 2010–2011 and 2016–2017 to 2017–2018). Biochemical oxygen demand, nitrates, total phosphorus, fecal coliforms, and total suspended solids were the variables that mainly explained the effects of the agricultural activities on water quality. The proposed water quality index included these unweighted variables, which allowed for the pre-sowing and post-harvest to be differentiated, as well as the degree of diversification. Therefore, the proposed WQI constitutes a tool that can be used to evaluate the water quality in an agricultural basin. Likewise, it can be used to select agricultural sequences that generate the least possible impacts on the associated water resources.     

Evaluation of aerosol sources at European high altitude background sites with trajectory statistical methods

This study has investigated the influence of synoptic weather patterns and long-range transport episodes on the concentrations of several compounds related to different aerosol sources (EC, OC, SO₄^2?, Ca²⁺, Na⁺, K⁺, ²¹⁰Pb, levoglucosan and dicarboxylic acids) registered in PM10 or PM2.5 aerosol samples collected at three remote background sites in central Europe. Air mass back-trajectories arriving at these sites have been analysed by statistical methods. Firstly, air mass back-trajectories have been grouped into clusters. Each cluster corresponds to specific meteorological scenarios, which were extracted and discussed. Finally, redistributed concentration fields have been computed to identify the main potential source regions of the different key aerosol components. A marked seasonal pattern is observed in the occurrence of the different clusters, with fast westerly and northerly Atlantic flows during winter and weak circulation flows in summer. Spring and fall were characterised by advection of moderate flows from northeastern and eastern Europe. Significant inter-cluster differences were observed for concentrations of receptor aerosol components, with the highest concentrations of EC, OC, SO₄^2?, K⁺ and ²¹⁰Pb associated with local and mesoscale aerosol sources located over central Europe related to enhanced photochemical processes. Emissions produced by fossil fuel and biomass burning processes from the Baltic countries, Byelorussia, western regions of Russia and Kazakhstan in spring and fall also contribute to elevated levels of EC, OC, SO₄^2?, K⁺ and ²¹⁰Pb. In the summer period long-range transport episodes of mineral dust from North-African deserts were also frequently detected, which caused elevated concentrations of coarse Ca²⁺ at sites. The baseline aerosol concentrations in central Europe at the high altitude background sites were registered in winter, with the exception of coarse Na⁺. While the relatively high concentrations of Na⁺ can be explained by sea salt advected from the Atlantic, the low levels of other aerosol components are caused by efficient aerosol scavenging associated to advections of Atlantic air masses, as well as lower emissions of these species over the Atlantic compared to those over the European continent and very limited vertical air mass exchange over the continent.     

Influence of boundary conditions on CMAQ simulations over the Iberian Peninsula

The influence of chemical boundary conditions (BC) on the response of the Community Multiscale Air Quality (CMAQ) model over the Iberian Peninsula was investigated in this study. Three strategies to supply boundary conditions in the context of the Integrated Assessment Modelling System for the Iberian Peninsula (SIMCA) were tested. Alternative methods consist in providing BC from (1) fixed, time-independent, concentration profiles, (2) concentrations predicted in a CMAQ mother domain (48 km, 1 h resolution) and (3) concentration values from the GEOS-Chem chemical-transport global model (2 × 2.5°, 3 h resolution). High resolution (3 km) simulated concentrations of the main pollutants (NO₂, NO, SO₂, O₃, PM₁₀ and PM_2.5) were compared through a comprehensive statistical analysis including observational data from 165 monitoring stations all over the Iberian Peninsula. It was found that model sensitivity to BC for nitrogen and sulphur oxides was limited, being restricted to the vicinity of model boundaries. However, significant domain-wide differences were found when modelling ozone and PM depending on the BC provided to run the tests. Although model performance was affected by spatial and seasonal factors, the results indicate that model-derived, dynamic BC improved CMAQ predictions when compared to those based on static concentrations prescribed in the boundaries. Aggregated statistics suggest that the GEOS-Chem produced the best results for O₃ and PM_2.5 while NO₂ and PM₁₀ were slightly better predicted under the CMAQ nesting approach. Besides the statistical evaluation some other relevant issues in the context of Integrated Assessment Modelling (IAM) are discussed to gain a better insight into the suitability of the methods analyzed and limitations of downscaling methods. Despite being useful to get a better understanding of the role of BC in SIMCA, this study contributed to highlight model deficiencies and therefore to point out future research needs to improve IAM activities in the Iberian Peninsula.     

Polycyclic aromatic hydrocarbons in air on small spatial and temporal scales – II. Mass size distributions and gas-particle partitioning

Polycyclic aromatic hydrocarbons (PAHs) were measured together with inorganic air pollutants at two urban sites and one rural background site in the Banja Luka area, Bosnia and Hercegovina, during 72 h in July 2008 using a high time resolution (5 samples per day) with the aim to study gas-particle partitioning, aerosol mass size distributions and to explore the potential of a higher time resolution (4 h-sampling).In the particulate phase the mass median diameters of the PAHs were found almost exclusively in the accumulation mode (0.1–1.0 μm of size). These were larger for semivolatile PAHs than for non-volatile PAHs. Gas-particle partitioning of semivolatile PAHs was strongly influenced by temperature. The results suggest that the Junge–Pankow model is inadequate to explain the inter-species variation and another process must be significant for phase partitioning which is less temperature sensitive than adsorption. Care should be taken when interpreting slopes m of plots of the type log K_p = m log p_L⁰ + b based on 24 h means, as these are found sensitive to the time averaging, i.e. tend to be higher than when based on 12 h-mean samples.     

An urban emissions inventory for South America and its application in numerical modeling of atmospheric chemical composition at local and regional scales

This work describes the development of an urban vehicle emissions inventory for South America, based on the analysis and aggregation of available inventories for major cities, with emphasis on its application in regional atmospheric chemistry modeling. Due to the limited number of available local inventories, urban emissions were extrapolated based on the correlation between city vehicle density and mobile source emissions of carbon monoxide (CO) and nitrogen oxides (NOx). Emissions were geographically distributed using a methodology that delimits urban areas using high spatial resolution remote sensing products. This numerical algorithm enabled a more precise representation of urban centers. The derived regional inventory was evaluated by analyzing the performance of a chemical weather forecast model in relation to observations of CO, NOx and O₃ in two different urban areas, São Paulo and Belo Horizonte. The gas mixing ratios simulated using the proposed regional inventory show good agreement with observations, consistently representing their hourly and daily variability. These results show that the integration of municipal inventories in a regional emissions map and their precise distribution in fine scale resolutions are important tools in regional atmospheric chemistry modeling.