Concept: Cation exchange capacity
In this study, the efficiency of six ion exchange resins to reduce the dissolved organic matter (DOM) from a biologically treated newsprint mill effluent was evaluated and the dominant removal mechanism of residual organics was established using advanced organic characterisations techniques. Among the resins screened, TAN1 possessed favourable Freundlich parameters, high resin capacity and solute affinity, closely followed by Marathon MSA and Marathon WBA. The removal efficiency of colour and lignin residuals was generally good for the anion exchange resins, greater than 50% and 75% respectively. In terms of the DOM fractions removal measured through liquid chromatography-organic carbon and nitrogen detector (LC-OCND), the resins mainly targeted the removal of humic and fulvic acids of molecular weight ranging between 500 and 1000gmol(-1), the portion expected to contribute the most to the aromaticity of the effluent. For the anion exchange resins, physical adsorption operated along with ion exchange mechanism assisting to remove neutral and transphilic acid fractions of DOM. The column studies confirmed TAN1 being the best of those screened, exhibited the longest mass transfer zone and maximum treatable volume of effluent. The treatable effluent volume with 50% reduction in dissolved organic carbon (DOC) was 4.8 L for TAN1 followed by Marathon MSA - 3.6L, Marathon 11 - 2.0L, 21K-XLT - 1.5L and Marathon WBA - 1.2L. The cation exchange resin G26 was not effective in DOM removal as the maximum DOC removal obtained was only 27%. The resin capacity could not be completely restored for any of the resins; however, a maximum restoration up to 74% and 93% was achieved for TAN1 and Marathon WBA resins. While this feasibility study indicates the potential option of using ion exchange resins for the reclamation of paper mill effluent, the need for improving the regeneration protocols to restore the resin efficiency is also identified. Similarly, care should be taken while employing LC-OCND for characterising resin-treated effluents, as the resin degradation is expected to contribute some organic carbon moieties misleading the actual performance of resin.
Imidazolium and quaternary ammonium-functionalized poly(fluorenyl ether ketone sulfone)s were synthesized successfully with the same degree of cationic functionalization and identical polymer backbones for a comparative study of anion exchange membranes (AEMs) for solid-state alkaline membrane fuel cells (AMFCs). Both anion exchange membranes were synthesized using a new methyl-containing monomer that avoided the use of toxic chloromethylation reagents. The polymer chemical structures were confirmed by (1)H NMR and FTIR. The derived AEMs were fully characterized by water uptake, anion conductivity, stability under aqueous basic conditions, and thermal stability. Interestingly, both the cationic groups and the polymer backbone were found to be degraded in 1 M NaOH solution at 60 °C over 48 h as measured by changes of ion exchange capacity and intrinsic viscosity. Imidazolium-functionalized poly(fluorenyl ether ketone sulfone)s had similar aqueous alkaline stability to quaternary ammonium-functionalized materials at 60 °C but much lower stability at 80 °C. This work demonstrates that quaternary ammonium and imidazolium cationic groups are not stable on poly(arylene ether sulfone) backbones under relatively mild conditions. Additionally, the poly(arylene ether sulfone) backbone, which is one of the most common polymers used in ion exchange membrane applications, is not stable in the types of molecular configurations analyzed.
Microbial fuel cells (MFCs) generate electricity from waste but to date the technology’s development and scale-up has been held-up by the need to incorporate expensive materials. A costly but vital component is the ion exchange membrane (IEM) which conducts protons between the anode and cathode electrodes. The current study compares natural rubber as an alternative material to two commercially available IEMs. Initially, the material proved impermeable to protons, but gradually a working voltage was generated that improved with time. After 6 months, MFCs with natural rubber membrane outperformed those with anion exchange membrane (AEM) but cation exchange membrane (CEM) produced 109 % higher power and 16 % higher current. After 11 months, polarisation experiments showed a decline in performance for both commercially available membranes while natural rubber continued to improve and generated 12 % higher power and 54 % higher current than CEM MFC. Scanning electron microscope images revealed distinct structural changes and the formation of micropores in natural latex samples that had been employed as IEM for 9 months. It is proposed that the channels and micropores formed as a result of biodegradation were providing pathways for proton transfer, reflected by the steady increase in power generation over time. These improvements may also be aided by the establishment of biofilms that, in contrast, caused declining performance in the CEM. The research demonstrates for the first time that the biodegradation of a ubiquitous waste material operating as IEM can benefit MFC performance while also improving the reactor’s lifetime compared to commercially available membranes.
We studied forest monitoring data collected at permanent plots in Italy over the period 2000-2009 to identify the possible impact of nitrogen (N) deposition on soil chemistry, tree nutrition and growth. Average N throughfall (N-NO3 +N-NH4 ) ranged between 4 and 29 kg ha(-1) yr(-1) , with Critical Loads (CLs) for nutrient N exceeded at several sites. Evidence is consistent in pointing out effects of N deposition on soil and tree nutrition: topsoil exchangeable base cations (BCE) and pH decreased with increasing N deposition, and foliar nutrient N ratios (especially N : P and N : K) increased. Comparison between bulk openfield and throughfall data suggested possible canopy uptake of N, levelling out for bulk deposition >4-6 kg ha(-1) yr(-1) . Partial Least Square (PLS) regression revealed that - although stand and meteorological variables explained the largest portion of variance in relative basal area increment (BAIrel 2000-2009) - N-related predictors (topsoil BCE, C : N, pH; foliar N-ratios; N deposition) nearly always improved the BAIrel model in terms of variance explained (from 78.2 to 93.5%) and error (from 2.98 to 1.50%). N deposition was the strongest predictor even when stand, management and atmosphere-related variables (meteorology and tropospheric ozone) were accounted for. The maximal annual response of BAIrel was estimated at 0.074-0.085% for every additional kgN. This corresponds to an annual maximal relative increase of 0.13-0.14% of carbon sequestered in the above-ground woody biomass for every additional kgN, i.e. a median value of 159 kgC per kgN ha(-1) yr(-1) (range: 50-504 kgC per kgN, depending on the site). Positive growth response occurred also at sites where signals of possible, perhaps recent N saturation were detected. This may suggest a time lag for detrimental N effects, but also that, under continuous high N input, the reported positive growth response may be not sustainable in the long-term.
High-quality formamidinium lead iodide (FAPbI3) perovskite thin films are fabricated via organic cation exchange. With ammonia lead iodide (NH4PbI3) as the starting material, the NH4(+) in NH4PbI3 could be gradually substituted by FA(+) in formamidine acetate (FA-Ac) and simultaneously transformed to the pure phase α-FAPbI3 at elevated temperature.
In mature soils, plant species and soil type determine the selection of root microbiota. Which of these two factors drives rhizosphere selection in barren substrates of developing desert soils has, however, not yet been established. Chronosequences of glacier forelands provide ideal natural environments to identify primary rhizosphere selection factors along the changing edaphic conditions of a developing soil. Here, we analyze changes in bacterial diversity in bulk soils and rhizospheres of a pioneer plant across a High Arctic glacier chronosequence. We show that the developmental stage of soil strongly modulates rhizosphere community assembly, even though plant-induced selection buffers the effect of changing edaphic factors. Bulk and rhizosphere soils host distinct bacterial communities that differentially vary along the chronosequence. Cation exchange capacity, exchangeable potassium, and metabolite concentration in the soil account for the rhizosphere bacterial diversity. Although the soil fraction (bulk soil and rhizosphere) explains up to 17.2% of the variation in bacterial microbiota, the soil developmental stage explains up to 47.7% of this variation. In addition, the operational taxonomic unit (OTU) co-occurrence network of the rhizosphere, whose complexity increases along the chronosequence, is loosely structured in barren compared with mature soils, corroborating our hypothesis that soil development tunes the rhizosphere effect.
This paper describes the technical development and accuracy assessment of the most recent and improved version of the SoilGrids system at 250m resolution (June 2016 update). SoilGrids provides global predictions for standard numeric soil properties (organic carbon, bulk density, Cation Exchange Capacity (CEC), pH, soil texture fractions and coarse fragments) at seven standard depths (0, 5, 15, 30, 60, 100 and 200 cm), in addition to predictions of depth to bedrock and distribution of soil classes based on the World Reference Base (WRB) and USDA classification systems (ca. 280 raster layers in total). Predictions were based on ca. 150,000 soil profiles used for training and a stack of 158 remote sensing-based soil covariates (primarily derived from MODIS land products, SRTM DEM derivatives, climatic images and global landform and lithology maps), which were used to fit an ensemble of machine learning methods-random forest and gradient boosting and/or multinomial logistic regression-as implemented in the R packages ranger, xgboost, nnet and caret. The results of 10-fold cross-validation show that the ensemble models explain between 56% (coarse fragments) and 83% (pH) of variation with an overall average of 61%. Improvements in the relative accuracy considering the amount of variation explained, in comparison to the previous version of SoilGrids at 1 km spatial resolution, range from 60 to 230%. Improvements can be attributed to: (1) the use of machine learning instead of linear regression, (2) to considerable investments in preparing finer resolution covariate layers and (3) to insertion of additional soil profiles. Further development of SoilGrids could include refinement of methods to incorporate input uncertainties and derivation of posterior probability distributions (per pixel), and further automation of spatial modeling so that soil maps can be generated for potentially hundreds of soil variables. Another area of future research is the development of methods for multiscale merging of SoilGrids predictions with local and/or national gridded soil products (e.g. up to 50 m spatial resolution) so that increasingly more accurate, complete and consistent global soil information can be produced. SoilGrids are available under the Open Data Base License.
Micro-patterned anion exchange membranes (AEM) have been 3D printed via a photoinitiated free radical polymerization and quaternization process. The photocurable formulation, consisting of diurethane dimethacrylate (DUDA), poly(ethylene glycol) diacrylate (PEGDA), dipentaerythritol penta-/hexa- acrylate, and 4-vinylbenzyl chloride (VBC), was directly cured into patterned films using a custom 3D photolithographic printing process similar to stereolithography. Measurements of water uptake, permselectivity, and ionic resistance were conducted on the quaternized poly(DUDA-co-PEGDA-co-VBC) sample series to determine their suitability as ion exchange membranes. The water uptake of the polymers increased as the ion exchange capacity (IEC) increased due to greater quaternized VBC content. Samples with IEC values between 0.98 to 1.63 meq/g were synthesized by varying the VBC content from 15 to 25 wt%. The water uptake was sensitive to the PEGDA content in the polymer resulting in water uptake values ranging from 85 to 410 wt% by varying PEGDA fractions from 0 to 60 wt%. The permselectivity of the AEM samples decreased from 0.91 (168 wt%, 1.63 meq/g) to 0.85 (410 wt%, 1.63 meq/g) with increasing water uptake and to 0.88 (162 wt%, 0.98 meq/g) with decreasing IEC. Permselectivity results were relatively consistent with the general understanding of the permselectivity correlation with the water uptake and ion content of the membrane. Lastly, it was revealed that the ionic resistance of patterned membranes was lower than that of flat membranes with the same material volume. A parallel resistance model was used to explain the patterning influence on the overall measured ionic resistance. This model may provide a way to maximize the ion exchange membrane performance by optimizing surface patterns without chemical modification to the membrane.
This study describes the validation and application of two independent analytical methods for the determination of glyphosate in breast milk. They are based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS), respectively. For LC-MS/MS, sample preparation involved an ultra-filtration followed by chromatography on an anion exchange column. The analysis by GC-MS/MS involved an extraction step, clean-up on a cation exchange column and derivatization with heptafluorobutanol and trifluoroacetic acid anhydride. Both methods were newly developed for breast milk and are able to quantify glyphosate residues at concentrations as low as 1 ng/mL. The methods were applied to quantify glyphosate levels in 114 breast milk samples, which had been collected from August to September of 2015 in Germany. The mothers participated at their own request and thus do not form a representative sample. In none of the investigated samples were glyphosate residues above the limit of detection found.
Ion exchange at charged solid-liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here we report temporal variation in the distribution of Rb(+) species at the muscovite (001)-water interface during exchange with Na(+). Time-resolved resonant anomalous X-ray reflectivity measurements at 25 °C reveal that Rb(+) desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb(+) slowly transforms to a less stable outer-sphere Rb(+). In contrast, Rb(+) adsorption is about twice as fast, proceeding from Rb(+) in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55 °C shows that the pre-exponential factor for desorption is significantly smaller than that for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface.