TXRF analysis of soils and sediments to assess environmental contamination

Total reflection x-ray fluorescence spectroscopy (TXRF) is proposed for the elemental chemical analysis of crustal environmental samples, such as sediments and soils. A comparative study of TXRF with respect to flame atomic absorption spectroscopy and inductively coupled plasma optical emission spectroscopy was performed. Microwave acid digestion and suspension preparation methods are evaluated. A good agreement was found among the results obtained with different spectroscopic techniques and sample preparation methods for Cr, Mn, Fe, Ni, Cu, and Zn. We demonstrated that TXRF is suitable for the assessment of environmental contamination phenomena, even if the errors for Pb, As, V, and Ba are ingent.     

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.     

Novel imazethapyr detoxification applying advanced oxidation processes

Different degradation methods have been applied to assess the suitability of advanced oxidation process (AOPs) to promote mineralization of imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid], a widely used imidazolinone class herbicide, the persistence of which has been demonstrated in surface and ground waters destined to human uses. Independent of the oxidation process assessed, the decomposition of imazethapyr always followed a pseudo-first order kinetic. The direct UV-irradiation (UV) of the herbicide as well as its oxidation with ozone (O?), and hydrogen peroxide tied to UV-irradiation (H?O?/UV) were sufficiently slow to permit the identification of intermediate products, the formation pathway of which has been proposed. Ozonation joined to UV-irradiation (O?/UV), ozonation joined to titanium dioxide photo-catalysis (TiO?/UV+O?), sole photo-catalysis (TiO?/UV), and photo-catalysis reinforced with hydrogen peroxide-oxidation (TiO?/UV+H?O?) were characterized by a faster degradation and rapid formation of a lot of small molecules, which were quickly degraded to complete mineralization. The most effective oxidation methods were those using titanium dioxide photo-catalysis enhanced either by ozonation or hydrogen peroxide. Most of all, these last processes were useful to avoid the development of dangerous by-products.     

Effect of the veterinary ionophore monensin on the structure and activity of a tropical soil bacterial community

Abstract

Monensin (MON) is a coccidiostat used as a growth promoter that can reach the environment through fertilization with manure from farm animals. To verify whether field-relevant concentrations of this drug negatively influence the structure and activity of tropical soil bacteria, plate counts, CO₂ efflux measurements, phospholipid fatty acids (PLFA) and community-level physiological profiling (CLPP) profiles were obtained for soil microcosms exposed to 1 or 10?mg kg^?1 of MON across 11?days. Although 53% (1?mg kg^?1) to 40% (10?mg kg^?1) of the MON concentrations added to the microcosms dissipated within 5?days, a subtle concentration-dependent decrease in the number of culturable bacteria (<1 log CFU g^?1), reduced (?20 to ?30%) or exacerbated (+25%) soil CO₂ effluxes, a marked shift of non-bacterial fatty acids, and altered respiration of amines (1.22-fold decrease) and polymers (1.70-fold increase) were noted in some of the treatments. These results suggest that MON quickly killed some microorganisms and that the surviving populations were selected and metabolically stimulated. Consequently, MON should be monitored in agronomic and environmental systems as part of One Health efforts.     

Soil pH effects on the interactions between dissolved zinc,non-nano- and nano-ZnO with soil bacterial communities

Zinc oxide nanoparticles (ZnO NPs) are used in an array of products and processes, ranging from personal care products to antifouling paints, textiles, food additives, antibacterial agents and environmental remediation processes. Soils are an environment likely to be exposed to manmade nanoparticles due to the practice of applying sewage sludge as a fertiliser or as an organic soil improver. However, understanding on the interactions between soil properties, nanoparticles and the organisms that live within soil is lacking, especially with regards to soil bacterial communities. We studied the effects of nanoparticulate, non-nanoparticulate and ionic zinc (in the form of zinc chloride) on the composition of bacterial communities in soil with a modified pH range (from pH 4.5 to pH 7.2). We observed strong pH-dependent effects on the interaction between bacterial communities and all forms of zinc, with the largest changes in bacterial community composition occurring in soils with low and medium pH levels (pH 4.8 and 5.9). The high pH soil (pH 7.2) was less susceptible to the effects of zinc exposure. At the highest doses of zinc (2500 mg/kg dw soil), both nano and non-nano particulate zinc applications elicited a similar response in the soil bacterial community, and this differed significantly to the ionic zinc salt treatment. The results highlight the importance of considering soil pH in nanotoxicology studies, although further work is needed to determine the exact mechanisms controlling the toxicity and fate and interactions of nanoparticles with soil microbial communities.     

First inter-laboratory comparison exercise for the determination of anticancer drugs in aqueous samples

The results of an inter-laboratory comparison exercise to determine cytostatic anticancer drug residues in surface water, hospital wastewater and wastewater treatment plant effluent are reported. To obtain a critical number of participants, an invitation was sent out to potential laboratories identified to have the necessary knowledge and instrumentation. Nine laboratories worldwide confirmed their participation in the exercise. The compounds selected (based on the extent of use and laboratories capabilities) included cyclophosphamide, ifosfamide, 5-fluorouracil, gemcitabine, etoposide, methotrexate and cisplatinum. Samples of spiked waste (hospital and wastewater treatment plant effluent) and surface water, and additional non-spiked hospital wastewater, were prepared by the organising laboratory (Jo?ef Stefan Institute) and sent out to each participant partner for analysis. All analytical methods included solid phase extraction (SPE) and the use of surrogate/internal standards for quantification. Chemical analysis was performed using either liquid or gas chromatography mass (MS) or tandem mass (MS/MS) spectrometry. Cisplatinum was determined using inductively coupled plasma mass spectrometry (ICP-MS). A required minimum contribution of five laboratories meant that only cyclophosphamide, ifosfamide, methotrexate and etoposide could be included in the statistical evaluation. z-score and Q test revealed 3 and 4 outliers using classical and robust approach, respectively. The smallest absolute differences between the spiked values and the measured values were observed in the surface water matrix. The highest within-laboratory repeatability was observed for methotrexate in all three matrices (CV?≤?12 %). Overall, inter-laboratory reproducibility was poor for all compounds and matrices (CV 27–143 %) with the only exception being methotrexate measured in the spiked hospital wastewater (CV?=?8 %). Random and total errors were identified by means of Youden plots.     

Ambient air pollution and term birth weight in Texas from 1998 to 2004

Previous studies have explored the association between air pollution levels and adverse birth outcomes such as lower birth weight. Existing literature suggests an association, although results across studies are not consistent. Additional research is needed to confirm the effect, investigate the exposure window of importance, and distinguish which pollutants cause harm.

We assessed the association between ambient pollutant concentrations and term birth weight for 1,548,904 births in TX from 1998 to 2004. Assignment of prenatal exposure to air pollutants was based on maternal county of residence at the time of delivery. Pollutants examined included particulate matter with aerodynamic diameter ≤10 and ≤2.5 µm (PM₁₀ and PM_2.5), sulfur dioxide (SO₂), nitrogen dioxide (NO₂), carbon monoxide (CO), and ozone (O₃). We applied a linear model with birth weight as a continuous variable. The model was adjusted for known risk factors and region. We assessed pollutant effects by trimester to identify biological exposure window of concern, and explored interaction due to race/ethnicity.

An interquartile increase in ambient pollutant concentrations of SO₂ and O₃ was associated with a 4.99-g (95% confidence interval [CI], 1.87–8.11) and 2.72-g (95% CI, 1.11–4.33) decrease in birth weight, respectively. Lower birth weight was associated with exposure to O₃ in the first and second trimester, whereas results were not significant for other pollutants by trimester. A positive association was exhibited for PM_2.5 in the first trimester. Effects estimates for PM₁₀ and PM_2.5 were inconsistent across race/ethnic groups.

Current ambient air pollution levels may be increasing the risk of lower birth weight for some pollutants. These risks may be increased for certain racial/ethnic groups. Additional research including consideration of improved methodology is needed to investigate these findings. Future studies should examine the influence of residual confounding.

Implications: This is one of the most comprehensive studies examining criteria air pollutants and lower birth weight in Texas. Our findings confirm results found previously for adverse effects of the air pollutant SO₂ on lower birth weight. Results from our study suggest that adverse pregnancy outcomes such as lower birth weight can occur even while maintaining air pollution levels below regulatory standards. Future studies should incorporate the assessment of differential pollutant exposure as well as effect estimates by race/ethnicity with individual and community-level social factors in order to enhance our understanding of how physical, social, and host factors influence birth outcomes.

Supplemental Materials: Supplementary information relating to characteristics of excluded births, distribution of air pollutant monitors by pollutant, and correlation coefficients of the air pollutants is available in the publisher's online edition of the Journal of the Air & Waste Management Association.     

Soil moisture determines the effectiveness of two urease inhibitors to decrease N<Subscript>2</Subscript>O emission

Among the mitigation strategies to prevent nitrogen (N) losses from ureic fertilizers, urease inhibitors (UIs) have been demonstrated to promote high N use efficiency by reducing ammonia (NH₃) volatilization. In the last few years, some field experiments have also shown its effectiveness in reducing nitrous oxide (N₂O) losses from fertilized soils under conditions of low soil moisture. An incubation experiment was carried out with the aim of assessing the main biotic mechanisms behind N₂O emissions once that the UIs N-(n-butyl) thiophosphoric triamid (NBPT) and phenil phosphorodiamidate (PPDA) were applied with Urea (U) under different soil moisture conditions (40, 60 and 80 % water-filled pore space, WFPS). In the same study we tried to analyze to what extent soil WFPS regulates the effect of these inhibitors on N₂O emissions. The use of PPDA in our study allowed us to compare the effect of NBPT with that of another commercially available urease inhibitor, aiming to see if the results were inhibitor-specific or not. Based on the results from this experiment, a WFPS (i.e. 60 %) was chosen for a second study (i.e. mesocosm experiment) aiming to assess the efficiency of the UIs to indirectly affect N₂O emissions through influencing the pool of soil mineral N. The N₂O emissions at 40 % WFPS were almost negligible, being significantly lower from all fertilized treatments than that produced at 60 and 80 % WFPS. When compared to U alone, NBPT+U reduced the N₂O emissions at 60 % WFPS but had no effect at 80 % WFPS. The application of PPDA significantly increased the emissions with respect to U at 80 % WFPS whereas no significant effect was found at 60 %. At 80 % WFPS, denitrification was the main source of N₂O emissions for all treatments. In the mesocosm study, the application of NBPT+U was an effective strategy to reduce N₂O emissions (75 % reduction compared to U alone), due to a lower soil ammonium (NH₄ ⁺) content induced by the inhibitor. These results suggest that adequate management of the UI NBPT could provide, under certain soil conditions, an opportunity for mitigation of N₂O emissions from fertilized soils.     

What matters for work engagement? A diary study on resources and the benefits of selective optimization with compensation for state work engagement

This diary study addresses the benefits of employees' daily use of selective optimization with compensation (SOC) for state work engagement. We hypothesized that day‐level SOC not only directly fosters work engagement but that SOC also reveals its beneficial effects for work engagement in interaction with both external and internal resources. Specifically, we proposed SOC substitutes for job control, role clarity, and state of being recovered, thus helping employees manage low daily levels of these resources. We tested our hypotheses with a sample of 138 employees who completed two daily surveys over a total of 545 workdays. Results of multilevel analyses revealed that SOC benefits work engagement in both proposed ways. First, day‐level SOC was positively related to state work engagement. Additionally, day‐level role clarity and state of being recovered predicted state work engagement, but day‐level job control did not. Second, SOC benefitted state work engagement by offsetting low levels of role clarity and being recovered, and by boosting job control in their respective relationships with work engagement. The results suggest that by using SOC at work, employees can actively enhance their own work engagement on a given workday. This knowledge provides promising starting points for the development of interventions.