Differential global profiling as a new analytical strategy for revealing micropollutant treatment by-products: application to ethinylestradiol and chlorination water treatment

The detection and structural elucidation of micropollutants treatment by-products are major issues to estimate efficiencies of the processes employed for drinking water production versus endocrine disruptive compounds contamination. This issue was mainly investigated at the laboratory scale and in high concentration conditions. However, potential by-products generated after chlorination can be influenced by the dilution factor employed in real conditions. The present study proposes a new methodology borrowed to the metabolomic science, using liquid chromatography coupled to high-resolution mass spectrometry, in order to reveal potential chlorination by-products of ethinylestradiol in spiked real water samples at the part-per-billion level (5 μg L⁻¹). Conventional targeted measurements first demonstrated that chlorination with sodium hypochlorite (0.8 mg L⁻¹) led to removals of ethinylestradiol over 97%. Then, the developed differential global profiling approach permitted to reveal eight chlorination by-products of EE2, six of them being described for the first time. Among these eight halogenated compounds, five have been structurally identified, demonstrating the potential capabilities of this new methodology applied to environmental samples.     

Modeling biogeochemical processes of phosphorus for global food supply

Harvests of crops, their trade and consumption, soil erosion, fertilization and recycling of organic waste generate fluxes of phosphorus in and out of the soil that continuously change the worldwide spatial distribution of total phosphorus in arable soils. Furthermore, due to variability in the properties of the virgin soils and the different histories of agricultural practices, on a planetary scale, the distribution of total soil phosphorus is very heterogeneous. There are two key relationships that determine how this distribution and its change over time affect crop yields. One is the relationship between total soil phosphorus and bioavailable soil phosphorus and the second is the relationship between bioavailable soil phosphorus and yields. Both of these depend on environmental variables such as soil properties and climate. We propose a model in which these relationships are described probabilistically and integrated with the dynamic feedbacks of P cycling in the human ecosystem. The model we propose is a first step towards evaluating the large-scale effects of different nutrient management scenarios. One application of particular interest is to evaluate the vulnerability of different regions to an increased scarcity in P mineral fertilizers. Another is to evaluate different regions’ deficiency in total soil phosphorus compared with the level at which they could sustain their maximum potential yield without external mineral inputs of phosphorus but solely by recycling organic matter to close the nutrient cycle.     

Microplastics affect assimilation efficiency in the freshwater amphipod <Emphasis Type="Italic">Gammarus fossarum</Emphasis>

An important issue in assessing microplastics is whether this newly emerging type of pollution affects freshwater invertebrates. This study was designed to examine the interactions between the amphipod Gammarus fossarum and two types of microplastics. To determine the ingestion and egestion of polyamide (PA) fibres (500 × 20 μm), amphipods were exposed to four concentrations (100, 540, 2680, 13,380 PA fibres cm^?2 base area of glass beakers) and four exposure times (0.5, 2, 8, 32 h) as well as four post-exposure times (1, 2, 4, 16 h). We demonstrate a positive correlation between concentration and ingestion of PA fibres. Fibres were found in the gut after 0.5 h of exposure. Egestion was rapid and the digestive tract was empty 16 h after exposure ended. To investigate whether polystyrene (PS) beads (1.6 μm) can be taken up in the epithelial cells of the gut and the midgut glands, four concentrations (500, 2500, 12,500, 60,000 PS beads mL^?1) were tested. Cryosections exhibited fluorescent PS beads only within the gut lumen. In a 28-day feeding experiment with both, fibres and beads, we studied the amphipod’s feeding rate, assimilation efficiency and wet weight change. The exposure to PA fibres (2680 PA fibres cm^?2 base area of glass beakers) significantly reduced the assimilation efficiency of the animals. While both tested polymer types are ingested and egested, PA fibres can impair the health and ecological functions of freshwater amphipods under continuous exposure.     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in a sediment–water system

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (¹⁴C-CfP) was studied for 28 days in lab assays using a sediment–water system derived from a German location. Mineralization was 5.21% of applied ¹⁴C after 28 days exhibiting a distinct lag phase until day 14 of incubation. Portions of radioactivity remaining in water phases decreased at moderate rate to 18.48% after 28 days; 62.46% were still detected in water after 14 days. Soxhlet extraction of the sediment using acetonitrile released 35.56% of applied ¹⁴C with day 28, while 33.99% remained as non-extractable residues. A remarkable increase of bound ¹⁴C was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with microbial activity of the sediment as determined by dimethyl sulfoxide reduction. Dissolved oxygen and pH value of water phases remained almost constant for 28 days. Analyses of Soxhlet extracts of the sediment and ethyl acetate extracts of water phases by radio-TLC and radio-HPLC revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed. DT₅₀ values (based on radio-HPLC) were below 1 day (CfP) and slightly above 28 days (Cf). Further metabolites were not detected. Fractionation of humic and non-humic components of the sediment demonstrated that CfP's non-extractable residues were predominantly associated with fulvic acids up to 14 days of incubation (3.36%), whereas after 28 days, the majority of radioactivity was found in the humin/mineral fraction (13.30% of applied ¹⁴C). Due to high-performance size-exclusion chromatography of the fulvic acids fraction derived from assays incubated for 28 days, this portion of ¹⁴C was firmly, possibly covalently bound to fulvic acids and did not consist of CfP or Cf. Using an isolation strategy comprising preincubation of sediment with CfP and mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the sediment examined. It grew on ¹⁴C-CfP as sole carbon source with evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and 16S rDNA sequence analysis. Its sequence exhibited high similarity with that of Nocardioides aromaticivorans strain H-1 (98.85%; DSM 15131, JCM 11674).     

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.     

Documentation of bioaerosol concentrations in an indoor composting facility in France

Bioaerosol concentrations were investigated in a totally indoor composting facility processing fermentable household and green wastes to assess their variability. Stationary samples were collected by filtration close to specific composting operations and then were analysed for cultivable mesophilic bacteria, thermophilic bacteria, mesophilic fungi, thermophilic fungi, endotoxins and total airborne bacteria (DAPI-staining). Indoor concentrations exceeded the background levels, between 500 and 5400 EU m(-3) for endotoxins, 10(4) and 10(6) CFU m(-3) for cultivable bacteria and generally below 10(5) CFU m(-3) for airborne cultivable fungi. No significant (p > 0.05) differences were observed between the indoor composting operations. Successive 30 minute bioaerosol samples were collected to investigate the variation of cultivable mesophilic microorganisms over the work shift. Concentrations of mesophilic bacteria and fungi varied up to 1 log unit depending on the time at which they were collected in the day. Total airborne particles, counted using an optical particle counter, were present at up to 10(8) particles m(-3) and several concentration peaks were noted. Values for total airborne bacteria were roughly 70-fold higher than cultivable bacteria. These results raise the question of the sampling strategy (duration of sampling; number of samples to be collected) used in similar studies. They provide new bioaerosol concentration data in a composting facility and suggest that the filtration sampling method might be a useful tool for exposure measurements in that occupational environment.     

Tolerance to agricultural pesticides of strains belonging to four genera of Rhizobiaceae

In order to determine their tolerance to pesticides, 122 strains of rhizobia isolated from different geographical regions, and belonging to the genera Rhizobium, Mesorhizobium, Sinorhizobium and Bradyrhizobium were tested against eight herbicides, four fungicides and five insecticides. Sensitivity to the pesticides was measured by using the filter paper disk method at four concentrations, 0.45, 4.5, 45 and 450 μg per disk. When the pesticides were used at 0.45 μg per disk, a concentration similar to that found when pesticides are applied under field conditions, no inhibition was observed. Strains growth was affected at concentrations of 45 and 450 μg pesticide per disk. These higher concentrations can be encountered when seeds are treated with pesticides. Pesticides tolerance level was correlated to pesticide function, i.e rhizobial strains were more tolerant to insecticides, followed by herbicides and then fungicides. Two fungicides, captan and mancozeb, inhibited the highest number of strains. Only one insecticide, carbaryl, affected the growth of some rhizobial strains. Strains isolated from the arctic (Mesorhizobium spp. and R. leguminosarum bv. viciae), a putative pesticides-free environment, were either less or equally affected by pesticides compared to strains isolated from agricultural regions.     

Late season pharmaceutical fate in wetland mesocosms with and without phosphorous addition

The fate of six human-use drugs was assessed and predicted in mesocosms designed to mimic shallow constructed wetlands during the onset of fall and senescence. Mesocosms were monitored for 28 days after the addition of carbamazepine, clofibric acid, fluoxetine and naproxen (nominal initial concentrations of 5 μg/L each), sulfamethoxazole, and sulfapyridine (nominal initial concentrations of 150 μg/L each), with and without phosphorous (P) addition at 1.6 mg/L. We hypothesized that addition of P would stimulate primary productivity and enhance removal of pharmaceuticals from the water column. Carbamazepine, clofibric acid, fluoxetine, and naproxen had half-lives of 8.7, 11, 1.5, and 2.5, and 8.6, 11.0, 1.4, and 2.5 days in treatments with and without P amendment, respectively. Sulfamethoxazole and sulfapyridine had half-lives of 17 and 4.9 days in mesocosms with P amendment and 17 and 4.7 days without amendment. A concurrent pulse of P with pharmaceuticals did not significantly enhance the removal of these compounds. Predicted half-lives from modeling efforts were consistent with observed values, with photolysis the greatest contributor to chemical attenuation.