Crops irrigated with reclaimed wastewater or grown in biosolids-amended soils may take up pharmaceuticals and personal care product ingredients (PPCPs) through their roots. The uptake pathways followed by PPCPs and the propensity for these compounds to bioaccumulate in food crops are still not well understood. In this critical review, we discuss processes expected to influence root uptake of PPCPs, evaluate current literature on uptake of PPCPs, assess models for predicting plant uptake of these compounds, and provide recommendations for future research, highlighting processes warranting study that hold promise for improving mechanistic understanding of plant uptake of PPCPs. We find that many processes that are expected to influence PPCP uptake and accumulation have received little study, particularly rhizosphere interactions, in planta transformations, and physicochemical properties beyond lipophilicity (as measured by Kow). Data gaps and discrepancies in methodology and reporting have so far hindered development of models that accurately predict plant uptake of PPCPs. Topics warranting investigation in future research include the influence of rhizosphere processes on uptake, determining mechanisms of uptake and accumulation, in planta transformations, the effects of PPCPs on plants, and the development of predictive models.
The effect of solution chemistry (pH, sorbate-to-sorbent ratio, ionic strength (/)) and reaction time on the sorption of tetracycline to the hydrous oxides of Al (HAO) and Fe (HFO) was examined. Sorption to HAO increased with increasing pH upto pH 7 (no such trend for HFO) above which it decreased at higher pH values for both the hydrous oxides. Experimental results indicate that ligand-promoted dissolution is occurring during tetracycline sorption to these hydrous oxides. Ligand-promoted dissolution was more significantfor HAO than HFO attributable to the difference in labile surface sites between these two sorbents. The ability of tetracycline to form strong complexes with Al and Fe will increase the solubility of these minerals. Sorption of tetracycline was quite rapid and equilibrium was achieved after 8 h. However, soluble metal (Me: Al or Fe) concentrations attained equilibrium only after 24 h. Ligand-promoted dissolution appears to be a two-step process; initially, 1:1 Me-tetracycline soluble complexes are formed and as the reaction progresses 2:1 complexes existed. Increasing / (from 0.01 to 0.5 M) decreased the sorption extent only at higher sorbate-to-sorbent ratios suggesting the dominance of inner-sphere type complexes at low equilibrium tetracycline concentrations. Spectroscopic evidence indicates that tricarbonylamide and carbonyl functional groups of tetracycline could be responsible for sorption to mineral surfaces. Our research findings will increase understanding of the environmental occurrence, fate, and transport characteristics of antibiotics, which are considered as emerging organic contaminants.
Cesium adsorption on the clay minerals vermiculite and montmorillonite is described as a function of surface coverage using extended X-ray adsorption fine structure spectroscopy (EXAFS). Cesium (Cs) possessed a variable coordination environment consisting of Cs-O distances between 3.2 and 4.3 A; however, disorder typical of the Cs coordination environments prevented the resolution of all oxygen shells. On the basis of the influence of Cs loading and exchangeability on this structural arrangement, we could recognize both inner-sphere and outer-sphere adsorption complexes. The shorter Cs-O bond distance belongs to outer-sphere complexes typical of hydrated ions. In inner-sphere complexes, partially or fully dehydrated Cs coordinates directly to siloxane groups of the clay minerals forming longer Cs-O bonds. The inner-sphere adsorption complexes may have occurred within the interlayer or at frayed edge sites and were less extractable than the outer-sphere complexed Cs. Both coordination number ratios and linear combination fitting of EXAFS spectra were useful in estimating the fractions of inner-sphere and outer-sphere adsorption complexes. Our results show that X-ray absorption spectroscopy (XAS), and particularly EXAFS, is a valuable technique for exploring the type of Cs binding in environmental samples.
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