Microalgae as Soft Permeable Particles.

The colloidal stability of non-motile algal cells in water drives their distribution in space. An accurate description of the interfacial properties of microalgae is therefore critical to understand how microalgae concentrations can change in their biotope or during harvesting processes. Here, we probe the surface charges of three unicellular algae─Chlorella vulgaris, Nannochloropsis oculata, and Tetraselmis suecica─through their electrophoretic mobility. Ohshima's soft particle theory describes the electrokinetic properties of particles covered by a permeable polyelectrolyte layer, a usual case for biological particles. The results appear to fit the predictions of Ohshima's theory, proving that all three microalgae behave electrokinetically as soft particles. This allowed us to estimate two characteristic parameters of the polyelectrolyte external layer of microalgae: the volume charge density and the hydrodynamic penetration length. Results were compared with transmission electron microscopy observations of the algal cells' surfaces, and in particular of their extracellular polymeric layer, which was identified with the permeable shell evidenced by electrophoretic measurements. Noticeably, the algal surface potentials estimated from electrophoretic mobility using the soft particle theory are less negative than the apparent zeta potentials. This finding indicates that electrostatics are expected to play a minor role in phenomena of environmental and industrial importance, such as microalgae aggregation or adhesion.

Phosphorus retention by granulated apatite: assessing maximum retention capacity, kinetics and retention processes.

Natural apatites have previously shown a great capacity for phosphate retention from wastewater. However, its fine particle size distribution may lead to a premature clogging of the filter. Accordingly, a granulated apatite product was developed and manufactured in order to control the particle size distribution of the media. Experiments were conducted on laboratory columns to assess their phosphorus retention capacity, to identify the processes involved in phosphorus retention and to evaluate their kinetic rates. The results showed phosphorus retention capacities of 10.5 and 12.4 g PO4-P·kg-1 and kinetic rate coefficients in the range of 0.63 and 0.23 h-1 involving lower values than those found for natural apatites in previous studies. Scanning Electron Microscopy images showed that apatite particles in the granules were embedded in the binder and were not readily accessible to act as seeds for calcium phosphate precipitation. The retention processes differ depending on the supersaturation of the solution with respect to calcium phosphate phases: at low calcium concentrations (69.8 ± 3.9 mg·L-1), hydroxyapatite precipitates fill up the porosity of the binder up to a depth of 100-300 µm from the granule surface; at higher calcium concentrations (112.7 ± 7.4 mg·L-1) precipitation occurs at the granule surface, forming successive layers of hydroxyapatite and carbonated calcium phosphates.

Hydrogeological control on carbon dioxide input into the atmosphere of the Chauvet-Pont d'Arc cave.

Carbon dioxide (CO2) concentration (CDC) is an essential parameter of underground atmospheres for safety and cave heritage preservation. In the Chauvet cave (South France), a world heritage site hosting unique paintings dated 36,000 years BP, a high-sensitivity monitoring, ongoing since 1997, revealed: 1) two compartments with a spatially uniform CDC, a large volume (A) (40,000 to 80,000 m3) with a mean value of 2.20 ± 0.01% vol. in 2016, and a smaller remote room (B) (2000 m3), with a higher mean value of 3.42 ± 0.01%; 2) large CDC annual variations with peak-to-peak amplitude of 2% and 1.6% in A and B, respectively; 3) long-term changes, with an increase of CDC and of its annual amplitude since 1997, then faster since 2013, reaching a maximum of 4.4% in B in 2017, decreasing afterwards. While a large effect of seasonal ventilation is ruled out, monitoring of seepage at two dripping points indicated that the main control of CDC seasonal reduction was transient infiltration. During periods of water deficit, calculated from surface temperature and rainfall, CDC systematically increased. The carbon isotopic composition of CO2, correlated with water excess, is consistent with a time-varying component of CO2 seeping from above. The CO2 flux, which is the primary driver of CDC in A and B, inferred using box modelling, was found to confirm the relationship between water excess and reduced CO2 flux into A, compatible with a more constant flux into B. A buoyancy-driven horizontal CO2 flow model in the vadose zone, hindered by water infiltration, is proposed. Similarly, pluri-annual and long-term CDC changes can likely be attributed to variations of water excess, but also to increasing vegetation density above the cave. As CDC controls the carbonate geochemistry, an increased variability of CDC raises concern for the preservation of the Chauvet cave paintings.

Variability of apparent and inherent optical properties of sediment-laden waters in large river basins - lessons from in situ measurements and bio-optical modeling.

We investigated the relationships between inherent and apparent optical properties (IOP and AOP, respectively) and suspended sediment concentrations (SSC) in the main Amazonian river waters. In situ measurements of SSC, remote sensing reflectance (Rrs), the diffuse light attenuation coefficient (Kd) and the total and non-algal particle (NAP) absorption coefficients (aTOT and aNAP, respectively) were conducted during three sampling trips along different streams of the Amazon River catchment (104 stations). The size distribution and chemical characteristics of the suspended sediment were also determined for 85 stations. We show that the particle size distribution (PSD) in the river water is best described by a segmented Junge power law distribution with a smaller slope value for the smallest particles (J1 = 2.4) and a larger slope value (J2 = 4.1) for the largest particles (> 10 µm). A strong relationship was found between AOPs and IOPs and SSC when the entire data set was considered. However, for the Madeira River, the primary Amazon River tributary in terms of suspended sediment discharge, a significant dispersion was detected for the Rrs - SSC relationship but not for the Kd - SSC relationship. This dispersion has been shown by a previous study, using MODIS data, to display a seasonal pattern, which we investigated in this study using Mie modeling calibrated with suspended sediment characteristics. In the Madeira River, suspended sediment had a finer distribution size and a different mineralogy (e.g., a greater smectite content and a lower kaolinite content) during the rising water stage. Spectral variations of the imaginary part n'(λ) of the refraction index also showed significant differences during the rising water stage. In contrast, other streams of the Amazon basin had very stable properties with respect to granulometry and mineralogy. Model simulations made possible to reproduce both field and satellite observations, showing that the Rrs hysteresis observed in the Madeira River in the near infrared was mainly due to n'(λ) seasonal variations, leading to a decrease of absorption during the rising water stage. Kd was shown to remain stable because of its strong dependency on scattering processes. The model was used to further understand how suspended sediment size distribution and refraction index drive the IOPs in large rivers: n'(λ) variations were shown to control primarily the reflectance variability; Rrs(850) presented limited variations as a function of PSD in the range typical of large rivers (J1 < 3) although it remained sensitive to particle mineralogical composition; Rrs(670) showed the opposite behavior with a higher sensitivity to PSD variation for coarser PSD. Finally, we demonstrate that the use of the Rrs ratio between the red and infrared channels allowed a reduction of the Rrs sensitivity in all cases, by an average of 50% with respect to changes in the mineral composition or size distribution of suspended sediment. In particular, the Rrs ratio varied by less than 5% for PSD representative of surface river waters.

Lead bioaccumulation in Opuntia ficus-indica following foliar or root exposure to lead-bearing apatite.

The contamination of edible leafy vegetables by atmospheric heavy metal-bearing particles is a major issue in environmental toxicology. In this study, the uptake of lead by cladodes of Opuntia ficus-indica (Ofi), traditionally used in Mexican cuisine and in livestock fodder, is investigated after a 4-months exposure of either cladodes or roots to synthetic Pb-fluorapatite particles. Atomic Absorption Spectroscopy (AAS) for the quantitative analysis of Pb levels, Scanning Electron Microscopy coupled with Energy Dispersive X-Ray Spectroscopy (SEM-EDX) for the examination of the cladode surface and fate of particles, and Micro-X-ray fluorescence (µXRF) measurements for elemental mapping of Pb in cladodes, were used. The results evidence that foliar contamination may be a major pathway for the transfer of Pb within Ofi cladodes. The stomata, areoles, and cuticle of cladode surface, play an obvious role in the retention and the incorporation of lead-bearing apatite, thus revealing the hazard of eating contaminated cladodes. The possibility of using series of successive cladodes for biomonitoring the atmospheric pollution in arid and semi-arid regions is also rapidly discussed.

Deciphering the aggregation mechanism of bacteria (Shewanella oneidensis MR1) in the presence of polyethyleneimine: Effects of the exopolymeric superstructure and polymer molecular weight.

Aggregation tests between bacteria and Polyethyleneimine (PEI) of low (600g/mol) and high (750,000g/mol) molecular weight were performed in order to address the physico-chemical mechanisms underlying the interactions between cationic polymer and bacterial membranes. The selected strain, Schewanella oneidensis MR-1, produces a lipopolysaccharide (LPS) of various lengths depending on the growth conditions. Optical density, bioaggregate size, electrophoretic mobility measurements, TEM and AFM observations, and cell lysis tests (crystal violet release), were collected to describe the PEI-mediated aggregation of LPS-O-antigen-free and LPS-O-antigen-decorated bacteria. The results show that PEI of low molecular weight (600g/mol) fails to aggregate bacteria, whereas PEIs of higher molecular weight (60,000 and 750,000g/mol) lead to flocculation at low polymer concentrations. In addition, the LPS-O antigen bacterial superstructure is shown to act as a protective barrier, thus delaying the harmful effects of the cationic polymer. Despite this protection, the interaction of bacterial membranes with increasing concentrations of PEI leads to a series of deleterious processes including biosurface modification (peeling, membrane permeabilization and/or lysis), aggregation of bacterial cells, and complexation of PEI with both released biosurface fragments and cytoplasmic residues issued from lysis.

Potential of Opuntia ficus-indica for air pollution biomonitoring: a lead isotopic study.

Opuntia ficus-indica (Ofi) is a long-domesticated cactus that is widespread throughout arid and semiarid regions. Ofi is grown for both its fruits and edible cladodes, which are flattened photosynthetic stems. Young cladodes develop from mother cladodes, thus forming series of cladodes of different ages. Therefore, successive cladodes may hold some potential for biomonitoring over several years the local atmospheric pollution. In this study, cladodes, roots, dust deposited onto the cladodes, and soil samples were collected in the vicinity of three heavily polluted sites, i.e., a fertilizer industry, the road side of a highway, and mine tailings. The lead content was analyzed using atomic absorption spectroscopy (AAS) and inductively coupled plasma-mass spectrometry (ICP-MS). Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX) was used to characterize the cladode surfaces and the nature of dust deposit, and the lead isotopes were analyzed to identify the origin of Pb. The results show that (i) Ofi readily bioaccumulates Pb, (ii) the lead isotopic composition of cladodes evidences a foliar pathway of lead into Ofi and identifies the relative contributions of local Pb sources, and (iii) an evolution of air quality is recorded with successive cladodes, which makes Ofi a potential biomonitor to be used in environmental and health studies.

Applying physicochemical approaches to control phosphogypsum heavy metal releases in aquatic environment.

One of the most important sources of solid waste in the Mediterranean Basin ecosystem originated from the phosphate fertilizer industries, which discharge phosphogypsum (PG) directly into aquatic environments or are stacked on stockpiles. The present study investigates metal release from PG under the influence of variable pH, increasing PG mass content, and complexing organic matter ligands. Major ions from PG leachates, grain size and charge, main functional groups along with metal leachability (Pb, Cd, Cr, Cu, and Zn) were determined using ion chromatography, laser diffraction, zetameter, Fourier transform infrared spectroscopy, and atomic absorption spectroscopy, respectively. The complete dissolution of PG recorded is at 2 g/L. Saturation and supersaturation with respect to PG may occur at concentrations of 3 and 4 g/L, respectively, revealing a clustering phenomenon leading to heavy metal encapsulation within the aggregates. Organic ligands such as citrate may trigger the cationic exchange within the PG suspension leading to ion release. As these factors are considered as specific process involving the release of contaminants from PG during storage under natural conditions, this study could set the foundations for PG remediation in aquatic environment. Organic ligands under controlled pH conditions could be utilized in treating fertilizer industrial wastes by taking into consideration the particularity of the receiving area, thus decreasing metal hazardous impact on natural media.

Coagulation of Na-montmorillonite by inorganic cations at neutral pH. A combined transmission X-ray microscopy, small angle and wide angle X-ray scattering study.

The coagulation of sodium montmorillonite by inorganic salts (NaNO3, Ca(NO3)2 and La(NO3)3) was studied by combining classical turbidity measurements with wide-angle-X-ray scattering (WAXS), small-angle-X-ray scattering (SAXS), and transmission X-ray microscopy (TXM). Using size-selected samples, such a combination, associated with an original quantitative treatment of TXM images, provides a true multiscale investigation of the formed structures in a spatial range extending from a few ångstroms to a few micrometers. We then show that, at neutral pH and starting with fully Na-exchanged samples, coagulation proceeds via the formation of stacks of particles with a slight mismatch between layers. These stacks arrange themselves into larger porous anisotropic particles, the porosity of which depends on the valence of the cation used for coagulation experiments. Face-face coagulation is clearly dominant under those conditions, and no evidence for significant face-edge coagulation was found. These structures appear to arrange as larger clusters, the organization of which should control the mechanical properties of the flocs.

Effects of fertilizer industry emissions on local soil contamination: a case study of a phosphate plant on the east Mediterranean coast.

Fugitive dust emission, transport and deposition from phosphate fertilizer industries may pose an environmental hazard to the surrounding environment, particularly to soil. This study is to evaluate such hazard by investigating the fate of airborne pollutants, their transfer from atmosphere to soil surface, and their contamination potential. Concentrations of elements were measured in soil samples. Elemental analyses were carried out using ICP-AES and ICP-MS. Analysis of speciation of trace elements, using a sequential extraction method, was performed on the plant's raw material (apatite), product and waste (phosphate fertilizer and phosphogypsum). A model estimating local atmospheric dry deposition was formulated. Statistical analyses were performed on sample data. Measured phosphorus accumulated considerably to the north-east of the plant, mainly due to the prevailing wind and associated dry deposition. Results exhibited considerably above-threshold enrichments in potentially toxic, bio-available trace elements (Cd, Zn) (2.5-6.9, 295-506 mg kg(-1)) and radionuclide (U, 20-98.69 mg kg(-1)) within a major deposition area. Speciation results revealed Zn and Cd occurring predominantly in mobile phases within the pollution source materials. Dry deposition calculation showed extensive input fluxes of Sr, Zn, Cr, U, Ni and Cd. Significant correlation was established between measured trace elements concentrations and their calculated deposition fluxes. Phosphorus species were the principal carriers of trace elements in soils. The phosphate industry poses a serious soil pollution hazard, with deposited contaminants being potentially hazardous to plants and groundwater. This study serves as a basis to assess the phosphate industry's risk impact on soil, while it introduces combined analytical methodologies for such assessment.

Polyethyleneimine-mediated flocculation of Shewanella oneidensis MR-1: impacts of cell surface appendage and polymer concentration.

In wastewater treatment plants, optimizing bacterial flocculation and bacterial sludge dewatering requires a detailed understanding of the concomitant biological and physico-chemical processes governing the action of flocculating agent on living cells. Here we investigate the interactions between polyethyleneimine (PEI, 60,000g/mol) and Shewanella oneidensis MR-1 lacking or not the lipopolysaccharide (LPS) O-antigen surface structure. Flocculation tests were performed on bacteria with/without LPS O-antigen after being exposed to 0-100mg/L PEI concentrations. Measurements of electrophoretic mobility and bacterial aggregates size were complemented by transmission electron micrographs and atomic force microscopy images. While low PEI concentrations (<20mg/L) lead to flocculation of both bare and LPS O-antigen-decorated bacterial strains, the lysis of bacterial membranes occurred at larger polymer concentrations for the latter, which highlights the protective role of LPS O-antigen against harmful PEI-mediated membrane alterations. Depending on polymer concentration, two types of bacterial aggregates are identified: one that solely integrates bacterial cells, and another that includes both cells and cell residues resulting from lysis (membrane and/or LPS fragments, and inner cell content materials). The latter is expected to significantly contribute to water entrapping in sludge and thus lower dewatering process efficiency.

Disruption of biofilms from sewage pipes under physical and chemical conditioning.

Biofilms grown inside two sewage collecting pipes located in industrial and residential areas are studied. Bacterial biomass inside three layers of biofilms was evaluated. Biofilm cohesion under different mixing rate and ionic strength was also investigated. Effects of physical and chemical parameters in the biofilms were evaluated by monitoring turbidity, chemical and biochemical oxygen demands. Extracted organic matter from biofilms was partitioned to polar, aromatic and saturated fractions using activated silica column chromatography. Results revealed that bacterial biomass growth depending on biofilm thickness and stratification. The most loaded stratum in bacterial biomass was the sewage-biofilm interface stratum that represented 51% of the total bacterial biomass. Stirring rate and ionic strength of mono- and bivalent salts showed a major influence in biofilm disruption. The stirring time enhanced the exchange dynamic and matter capture between biofilm fragments at the critical stirring rate 90 r/min. Sodium chloride showed the dispersing effect on biofilms in suspension, and decreased the BOD5 (biochemical oxygen demand) beyond the physiological salt concentration.

Characterization of activated sludge exopolymers from various origins: a combined size-exclusion chromatography and infrared microscopy study.

High-pressure size-exclusion liquid chromatography and infrared microscopy were coupled to investigate the molecular weight and nature of extracellular polymeric substances (EPS) from various activated sludges. Six main families of compounds (proteins, polysaccharides, organic acids, lipids, mineral phases) were found either as a single molecule or as associations. The molecular weight of proteins varied from small (10 kDa) to large (600 kDa) sizes, while all polysaccharides were smaller than 1 kDa. Association of different molecules implied the presence of species large in size. The EPS chromatographic fingerprints of sludge from various origins remained stable in normal operating conditions, but were drastically modified during settling crises. In poor settling conditions, the EPS with smaller molecular sizes always prevailed and large polymers were underrepresented. The EPS identified in activated sludge were collected in a chemical database which provides the basis for comparison of municipal and industrial wastewater treatment plants (WWTP).

Activated sludge exopolymers: separation and identification using size exclusion chromatography and infrared micro-spectroscopy.

Extracellular polymeric substances were extracted from activated sludge using a resin exchange method and analyzed. The separation and identification of EPS were carried out by size exclusion chromatography and Fourier transform infrared micro-spectroscopy. Chromatograms of extracted EPS exhibited seven peaks. Proteins varying in molecular weights from 670 to 45 kDa were present in all the peaks. Polysaccharides corresponding to molecular weights of approximately 1 and approximately 0.5 kDa were present in only three peaks. Strong association of polysaccharides and proteins was observed. Infrared results revealed the presence of one type of polysaccharide and two types of proteins (A and B). Proteins differed mainly in the length of their associated alkyl chains and in the ratio of ester/acidic functionalities.