On-line solid phase extraction and liquid chromatography/tandem mass spectrometry to quantify pharmaceuticals, pesticides and some metabolites in wastewaters, drinking, and surface waters

A simple on-line method was developed for the analysis of pharmaceuticals, pesticides and some metabolites in drinking, surface and wastewater samples. The technique is based on the use of on-line solid-phase extraction combined with liquid chromatography electrospray tandem mass spectrometry with positive electrospray ionization (LC-ESI(PI)-MS/MS). The injection of only 1 mL of filtered water sample is used with a total analysis time of 20 min, including the period required to flush the SPE cartridge with organic solvent and reconditioning the LC column. Method detection limits were in the range of 2 to 24 ng L(-1) for the compounds of interest, with recoveries from 87 to 110% in surface as well as wastewater samples. Matrix effects were observed for some compounds without exceeding more than 25%. All results displayed a good degree of reproducibility, with relative standard deviations (RSD) of less than 12% for all compounds. Moreover, at least 200 samples were analyzed without altering the performance of the pre-concentration column. This method was preferred over traditional off-line procedures because it minimizes tedious sample preparation, increases productivity and sample throughput. The analysis of various water and wastewater samples showed that caffeine, carbamazepine and atrazine could be detected in all the samples analysed and the selected compounds are always present in at least one of the sample types.     

Reactivity of the plant growth regulator paclobutrazol (cultar) with two tropical soils of the northeast semiarid region of Brazil

The reactivity of paclobutrazol (PBZ, a plant growth retardant) with a Yellow Ultisol and a Vertisol from the semiarid northeast region of Brazil was evaluated through batch sorption experiments and modeling. Although not instantaneous, the sorption kinetic of PBZ (pure and formulated) was fast (a few hours) in both soils. The sorption kinetics were well described by a second-order (dS(t)/dt=k(2)(S(e2)-S(t))(2)) but not by a first-order model. The sorption isotherms were found to be linear and the calculated K(D) values were 8.8 +/- 0.11 and 7.4 +/- 0.2 L kg(-1) for pure PBZ in the Ultisol and the Vertisol, respectively. The corresponding K(OC) values were 1275 +/- 34 (logK(OC) = 3.11) and 1156 +/- 49 (logK(OC) = 3.06) L kg(-1), respectively. Considering the very different texture of the two soils and the similar K(OC) values determined, these results showed that in both soils, the sorption of PBZ is dominantly controlled by organic matter, although some interactions of PBZ with iron oxides (goethite) were observed in the Ultisol. Based on these sorption parameters a low leachability potential of PBZ in soils is anticipated, as they correspond to a groundwater ubiquity score (GUS) ranging from 2.0 to 2.7, i.e., moderately to not mobile, in contradiction with the actual groundwater situation in Brazil. This work stresses the need to evaluate and predict the risk associated with aquifer contamination by this widely used plant growth regulator.     

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.     

Dynamical Allocation Method of Emission Rights of Pollutants by Viability Constraints Under Tychastic Uncertainty

This study proposes a method of dynamic decentralization by constraints and its associated software. It can be used to allocate pollutant emissions rights among the different polluters such that they achieve both given global and local emission thresholds not to be transgressed. Knowing the maximum growth rates of polluting emissions of each polluter in the worst case, this method provides the rule of a dynamic allocation of pollutant emissions rights as well as the required initial emissions of each polluters assuring that, whatever the growth rates of the emissions below the maximum growth rates, the resulting emissions will be, both globally and locally, under their thresholds. These guaranteed initial emissions supply each polluter with a measure of risk insurance. This problem, formulated as a “tychastic” regulated system with viability constraints, is solved with mathematical and algorithmic tools of viability theory and numerical results obtained by a dedicated software are presented.     

Fundamental insights on when social network data are most critical for conservation planning

As declines in biodiversity accelerate, there is an urgent imperative to ensure that every dollar spent on conservation counts toward species protection. Systematic conservation planning is a widely used approach to achieve this, but there is growing concern that it must better integrate the human social dimensions of conservation to be effective. Yet, fundamental insights about when social data are most critical to inform conservation planning decisions are lacking. To address this problem, we derived novel principles to guide strategic investment in social network information for systematic conservation planning. We considered the common conservation problem of identifying which social actors, in a social network, to engage with to incentivize conservation behavior that maximizes the number of species protected. We used simulations of social networks and species distributed across network nodes to identify the optimal state-dependent strategies and the value of social network information. We did this for a range of motif network structures and species distributions and applied the approach to a small-scale fishery in Kenya. The value of social network information depended strongly on both the distribution of species and social network structure. When species distributions were highly nested (i.e., when species-poor sites are subsets of species-rich sites), the value of social network information was almost always low. This suggests that information on how species are distributed across a network is critical for determining whether to invest in collecting social network data. In contrast, the value of social network information was greatest when social networks were highly centralized. Results for the small-scale fishery were consistent with the simulations. Our results suggest that strategic collection of social network data should be prioritized when species distributions are un-nested and when social networks are likely to be centralized.     

Rapid measurement of the yield stress of anaerobically-digested solid waste using slump tests

The anaerobic digestion of solid waste is usually performed using dry or semi-dry technology. Incoming waste and fermenting digestate are pasty media and thus, at the industrial scale, their suitability for pumping and mixing is a prerequisite at the industrial scale. However, their rheology has been poorly characterised in the literature because there is no suitable experimental system for analysing heterogeneous media composed of coarse particles. We have developed a practical rheometrical test, a “slump test”, for the analysis of actual digested solid waste. It makes it possible to estimate yield stress from the final slump height. From the slump behavior, we conclude that digestates behave as visco-elastic materials. The yield stress of different digested waste was measured between 200 and 800 Pa. We show that the media containing smaller particles or with higher moisture content are characterised by smaller yield stresses. This study thus demonstrates the impact of the origin of the digestate on the yield stress.     

Organic micropollutants’ distribution within sludge organic matter fractions explains their dynamic during sewage sludge anaerobic digestion followed by composting

The simultaneous fate of organic matter and 4 endocrine disruptors (3 polycyclic aromatic hydrocarbons (PAHs) (fluoranthene, benzo(b)fluoranthene, and benzo(a)pyrene) and nonylphenols (NP)) was studied during the anaerobic digestion followed by composting of sludge at lab-scale. Sludge organic matter was characterized, thanks to chemical fractionation and 3D fluorescence deciphering its accessibility and biodegradability. Total chemical oxygen demand (COD) removal was 41% and 56% during anaerobic digestion and composting, respectively. 3D fluorescence highlighted the quality changes of organic matter. During continuous anaerobic digestion, organic micropollutants’ removal was 22?±?14%, 6?±?5%, 18?±?9%, and 0% for fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, and nonylphenols, respectively. Discontinuous composting allowed to go further on the organic micropollutants’ removal as 34?±?8%, 31?±?20%, 38?±?10%, and 52?±?6% of fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, and nonylphenols were dissipated, respectively. Moreover, the accessibility of PAH and NP expressed by their presence in the various sludge organic matter fractions and its evolution during both treatments was linked to both the quality evolution of the organic matter and the physicochemical properties of the PAH and NP; the presence in most accessible fractions explained the amount of PAH and NP dissipated.

     

On-line greenhouse gas detection from soils and rock formations

Several on-site studies have been conducted on rock formations and soils where gases were collected into boreholes. The equipment consisted of packers isolating a chamber for gas collection. A pump allows gas transfer towards FT-IR sensors located at the surface. Such analytical approach shows several advantages for gas monitoring in boreholes: it allows variation detection with time of the partial pressure of gases; detection and evolution with time of the concentration of annex gases or markers; application to the injection and post-injection periods to determine possible deviations from a previously recorded baseline; and possible use of several boreholes in networks.