Chitosan/albumin/CaCO3 as mimics for membrane bioreactor fouling: genesis of structural mineralized-EPS-building blocks and cake layer compressibility

Membrane bioreactor biofouling is usually described as an extracellular matrix in which biopolymers, inorganic salts and active microbes co-exist. For that reason, biomineralization (BM) models can be useful to describe the spatial organization and environmental constraints within the referred scenario. BM arguments were utilized as background in order to (1) evaluate CaCO₃ influence on flux decline; pore blocking and cake layer properties (resistance, permeability and compressibility) in a wide range of Chitosan/Bovine serum albumin (BSA) mixtures during step-pressure runs and, (2) perform membrane autopsies in order to explore the genesis of mineralized extracellular building blocks (MEBB) during cake layer build up. Using low molecular weight chitosan (LC) and BSA, 2 L of 5 LC/BSA mixtures (0.25-1.85 ratio) were pumped to an external ultra filtration (UF) membrane (23.5 cm², hydrophobic, piezoelectric, 100 kDa as molecular weight cut-off). Eight different pressure steps (40 ± 7 to 540 ± 21 kPa) were applied. Each pressure step was held for 900 s. CaCO₃ was added to LC/BSA mixtures at 0.5, 1.5 and 3 mM in order to create MEBB during the filtration tests. Membrane autopsies were performed after the filtration tests using thermo gravimetric, scanning microscopy and specific membrane mass (mg cm⁻²) analyses. Biopolymer-CaCO₃ step-pressure filtration created compressible cake layers (with inner voids). The formation of an internal skeleton of MEBB may contribute to irreversible fouling consolidation. A hypothesis for MEBB genesis and development was set forth.     

Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection

The Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) has been validated for the extraction of 15 organochlorine pesticides (OCPs) in completely different matrices of traditional Chinese medicine (TCM). The method employed a rapid, simple and cost-effective procedure. The spiking levels for the recovery experiments were 0.1, 0.5 and 2.0 mg kg⁻¹. Mean recoveries mostly ranged between 76.0% and 114.0% (96.0% on average), and relative standard deviations (RSD) were generally below 10% (4.72% on average). Based on these results, the methodology has been proven to be highly efficient and robust and thus suitable for monitoring the MRL compliance of a wide range of commodity. The contamination status of 15 OCPs on 80 different TCMs marketed in China, and a total of 400 samples were also performed using a previously validated method. 15 OCPs were benzene hexachloride (BHC, including α-BHC, β-BHC, γ-BHC, δ-BHC), hexachlorobenzene, heptachlor, heptachlor epoxide, aldrin, p, p′-DDE, p, p′-DDD, o, p′-DDT, p, p′-DDT, mirex, endrin, dieldrin. This study indicates that the proposed method is useful for analyzing OCPs in TCM.     

Trade-offs between elimination and detoxification in rainbow trout and common bivalve molluscs exposed to metal stressors

The purpose of this paper was to examine trade-offs between elimination and detoxification in rainbow trout and three common bivalve molluscs (clam, oyster, and scallop) exposed to cadmium (Cd), copper (Cu), and zinc (Zn) based on recent reported experimental data. We incorporated metal influx threshold with subcellular partitioning to estimate rate constants of detoxification (k_d) and elimination (k₂). We found that the relationships between k₂ and k_d were negative for rainbow trout and positive for bivalve molluscs. However, the relationships between k_d and % metal in metabolically detoxified pool were found positive for rainbow trout and negative for bivalve molluscs. Our results also indicated that rainbow trout had higher accumulation (∼60-90%) in metabolically active pool when exposed to essential metals of Cu and Zn and had only 10-50% accumulation in response to non-essential metal of Cd. Based on a cluster analysis, this study indicated that similarity of physiological regulations among study species was found between Cd and Zn. Our study suggested that detoxification can be predicted by an elimination-detoxification scheme with the known elimination rate constant. We concluded that quantification of trade-offs between subcellular partitioning and detoxification provides valuable insights into the ecotoxicology of aquatic organisms and enhances our understanding of the subcellular biology of trace metals.     

Bromination of selected pharmaceuticals in water matrices

The bromination of five selected pharmaceuticals (metoprolol, naproxen, amoxicillin, phenacetin, and hydrochlorothiazide) was studied with these compounds individually dissolved in ultra-pure water. The apparent rate constants for the bromination reaction were determined as a function of the pH, obtaining the sequence amoxicillin > naproxen ? hydrochlorothiazide ≈ phenacetin ≈ metoprolol. A kinetic mechanism specifying the dissociation reactions and the species formed for each compound according to its pK_a value and the pH allowed the intrinsic rate constants to be determined for each elementary reaction. There was fairly good agreement between the experimental and calculated values of the apparent rate constants, confirming the goodness of the proposed reaction mechanism.In a second stage, the bromination of the selected pharmaceuticals simultaneously dissolved in three water matrices (a groundwater, a surface water from a public reservoir, and a secondary effluent from a WWTP) was investigated. The pharmaceutical elimination trend agreed with the previously determined rate constants. The influence of the main operating conditions (pH, initial bromine dose, and characteristics of the water matrix) on the degradation of the pharmaceuticals was established. An elimination concentration profile for each pharmaceutical in the water matrices was proposed based on the use of the previously evaluated apparent rate constants, and the theoretical results agreed satisfactorily with experiment. Finally, chlorination experiments performed in the presence of bromide showed that low bromide concentrations slightly accelerate the oxidation of the selected pharmaceuticals during chlorine disinfection.     

Motility of Pseudomonas aeruginosa in saturated granular media as affected by chemoattractant

To examine and quantify the effects of glass beads and chemoattractant on bacterial motility in granular media, we examined the motile behavior of P. aeruginosa in a saturated granular medium and quantified the effects of glass beads and the presence of a chemoattractant. By recording individual cell trajectories in microfluidic channels under a high-speed confocal microscope, we directly measured the cell's run direction and corresponding run-length, speed and turn angle. Bacterial run speed increased in the presence of chemoattractant in both aqueous and granular media. But it decreased in glass-beads compared to in aqueous media due to the restricted pore geometry and interactions between bacteria and grain surfaces. Notably, the relatively higher frequency distribution at turn angles of 170° decreased dramatically, while the smaller peak at 70° increased and became dominant on a bimodal distribution, showing more bacteria changed directions at smaller turn angles rather than reverse their swimming directions. Additionally, the presence of glass beads also decreased the chemotactic velocity and random motility by similar proportions due to the restrictive geometry and the interactions between bacteria and glass beads surface. Our study indicates that the swimming parameters measured from aqueous media cannot be directly adopted in models for predicting bacteria travel in granular media.     

Dietary uptake of polybrominated diphenyl ethers (PBDEs), occurrence and profiles, in aquacultured turbots (Psetta maxima) from Galicia, Spain

Polybromodiphenyl ethers (PBDEs) are one of the many toxic chemicals present in the environment and in the food we eat every day, being fish one of the main sources of persistent organic pollutants in our diet; like other lipid-related contaminants, they are of concern since they can bioaccumulate and biomagnify through the trophic chain. We published a study focused on the dietary uptake of dioxins and furans (PCDD/Fs) and dioxin-like polychlorobiphenyls (dl-PCBs) in a set of samples of Spanish farmed turbot (Blanco et al., 2007). In the present paper, we extend the study to PBDEs to provide more information about the uptake and transfer from feed to fish of halogenated contaminants. PBDEs in the feeds (2.35-4.76 ng g(-1)) were reflected in turbot fillets (0.54-2.05 ng g(-1)): predominant congeners were tetra-BDE 47, penta-BDEs 99 and 100. It is remarkable that tetra-BDE 49, accounting for only 2% in the feed, contributed to 15% of total PBDEs in turbot fillets. Dietary net accumulation values, 30-45%, showed that tri-, tetra-, penta- and hexa-BDEs were as efficiently transferred into turbot as dl-PCBs and tetra- and penta-chlorinated PCDD/Fs. Lipid-normalized biomagnification factors relating concentration in fish and in feed, BMFs>1 were obtained, except for BDE 209. BDE 49 accumulation, 90%, was possibly contributed by metabolism of higher brominated BDEs. Implication in aquaculture management is a need for uncontaminated fish feed to offer safe products.     

Effects of pH and ionic strength on sulfamethoxazole and ciprofloxacin transport in saturated porous media

Many antibiotics regarded as emerging contaminants have been frequently detected in soils and groundwater; however, their transport behaviors in soils remain largely unknown. This study examined the transport of two antibiotics, sulfamethoxazole (SMZ) and ciprofloxacin (CIP), in saturated porous media. Laboratory columns packed with quartz sand was used to test the effects of solution pH and ionic strength (IS) on their retention and transport. The results showed that these two antibiotics behaved differently in the saturated sand columns. In general, SMZ manifested a much higher mobility than CIP for all experimental conditions tested. Almost all SMZ transported through the columns within one pore volume in deionized water (i.e., pH=5.6, IS=0), but no CIP was detected in the effluents under the same condition after extended column flushing. Perturbations in solution pH (5.6 and 9.5) and IS (0 and 0.1M) showed no effect on SMZ transport in the saturated columns. When pH increased to 9.5, however, ~93% of CIP was eluted from the sand columns. Increase of IS from 0 to 0.1M also slightly changed the distribution of adsorbed CIP within the sand column at pH 5.6, but still no CIP was detected in the effluents. A mathematical model based on advection-dispersion equation coupled with equilibrium and kinetic reactions successfully simulated the transport of the antibiotics in water-saturated porous media with R(2)=0.99.     

Characterization of ACC deaminase-producing endophytic bacteria isolated from copper-tolerant plants and their potential in promoting the growth and copper accumulation of Brassica napus

One hundred Cu-resistant-endophytic bacteria were isolated from Cu-tolerant plants grown on Cu mine wasteland, of which, eight Cu-resistant and 1-aminocyclopropane-1-carboxylate (ACC) deaminase-producing endophytic bacteria were obtained based on the ACC deaminase activity of the bacteria and characterized with respect to metal resistance, production of ACC deaminase, indole-3-acetic acid (IAA) as well as siderophores and mineral phosphate solubilization. Ralstonia sp. J1-22-2, Pantoea agglomerans Jp3-3, and Pseudomonas thivervalensis Y1-3-9 with higher ACC deaminase activity (ranging from 213 to 370 μM α-ketobutyrate mg(-1)h(-1)) were evaluated for promoting plant growth and Cu uptake of rape grown in quartz sand containing 0, 2.5, and 5 mg kg(-1) of Cu in pot experiments. The eight bacteria were found to exhibit different multiple heavy metal resistance characteristics, to show different levels of ACC deaminase activity and to produce indole acetic acid. Seven bacteria produced siderophores and solubilized inorganic phosphate. Pot experiments showed that inoculation with the strains (J1-22-2, Jp3-3, and Y1-3-9) was found to increase the biomass of rape. Increases in above-ground tissue Cu contents of rape cultivated in 2.5 and 5 mg kg(-1) of Cu-contaminated substrates varied from 9% to 31% and from 3 to 4-fold respectively in inoculated-rape plants compared to the uninoculated control. The maximum Cu uptake of rape was observed after inoculation with P. agglomerans Jp3-3. The results show that metal-resistant and plant growth promoting endophytic bacteria play an important role in plant growth and Cu uptake which may provide a new endophytic bacterial-assisted phytoremediation of Cu-contaminated environment.     

Effects of compositional heterogeneity and nanoporosity of raw and treated biomass-generated soot on adsorption and absorption of organic contaminants

A biomass-generated soot was sequentially treated by HCl-HF solution, organic solvent, and oxidative acid to remove ash, extractable native organic matter (EOM), and amorphous carbon. The compositional heterogeneity and nano-structure of the untreated and treated soot samples were characterized by elemental analysis, thermal gravimetric analysis, BET-N₂ surface area, and electron microscopic analysis. Sorption properties of polar and nonpolar organic pollutants onto the soot samples were compared, and individual contributions of adsorption and absorption were quantified. The sorption isotherms for raw sample were practically linear, while were nonlinear for the pretreated-soot. The removal of EOM enhanced adsorption and reduced absorption, indicating that EOM served as a partitioning phase and simultaneously masked the adsorptive sites. By drastic-oxidation, the outer amorphous carbon and the inner disordered core of the soot particles were completely removed, and a fullerene-like nanoporous structure (aromatic shell) was created, which promoted additional π-π interaction between phenanthrene and the soot.     

粗MnSO4溶液中MnS2O6的去除条件研究

用软锰矿吸收SO2生成MnSO4时会伴随有副产物MnS2O6生成。产品中MnS2O6的存在会降低硫酸锰产品质量,同时会缓慢释放出SO2气体污染环境。本文用单因素实验方法研究了粗MnSO4溶液中MnS2O6的最优去除条件。研究结果显示,软锰矿用量为12.2 g,硫酸加入量为20 mL、反应温度100℃、反应时间3 h、搅拌速度500 r/min,MnS2O6的去除率可达91%以上。其最终产品能达到GB1622-1986一级品标准。