This study compared the ability of the lichen Evernia prunastri, chitin and chitosan to take up Cu2+ and Zn2+. It was hypothesized that chitin and chitosan have an accumulation capacity comparable to the lichen, so that these biopolymers could replace the use of E. prunastri for effective biomonitoring of Cu and Zn air pollution. Samples of the lichen E. prunastri, as well as chitin (from shrimps) and chitosan (from crabs), were incubated with Cu and Zn solutions at concentrations of 0 (control), 10, 25, 50, 75, and 100 µM and analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Metal concentrations accumulated by lichen, chitin and chitosan samples were strongly and linearly correlated with the concentrations in the treatment solutions. The lichen always showed significantly higher accumulation values compared to chitin and chitosan, which showed similar accumulation features. The outcomes of this study confirmed the great effectiveness of the lichen Evernia prunastri for environmental biomonitoring and showed that chitin and chitosan have a lower accumulation capacity, thus suggesting that although these biopolymers have the potential for replacing E. prunastri in polluted areas, their suitability may be limited in areas with intermediate or low pollution levels.
Chitin is an effective sorbent which can be used in environmental monitoring, beyond obvious applications in withholding metal-containing pollutants from wastewater- or nuclear fuel reprocessing flows, since background levels in (purified) chitin are very low except for a few metals (Fe, Cu, Al, Ti, and Zn). Since retention of Mx+ and their complexes on chitin depend on an oxidation state, and to a lesser extent the presence of possible ligands or co-ligands, partition between chitin samples exposed to sediment and those exposed to water can be changed by environmental factors such as local biota producing or absorbing/metabolizing effective ligands such as citrate or oxalate and by changes of redox potential. Thermodynamics are studied via log P, using calibration functions log P vs. 1/r or log P vs. Σσ (sum of Hammett parameters of ligand donor groups) for di- and trivalent elements not involved in biochemical activity (not even indirectly) and thus measuring “deviations” from expected values. These “deviations” can be due to input as a pollutant, biochemical use of certain elements, precipitation or (bio-induced reduction of SO42− or CO2) dissolution of solids in sediment. Biochemical processes which occur deep in sediment can be detected due to this effect. Data from grafted chitin (saturation within ≤ 10 min) and from outer surfaces of arthropods caught at the same site do agree well. Log P is more telling than total amounts retrieved. Future applications of these features of chitin are outlined.
There is strong adsorption of metal ions and their complexes to chitin, which depends on both the oxidation and complexation states of many of the said elements (whereas others display chemical reactions detectable via electrochemical methods while being retained by chitin); thus, ad- and desorption at ambient water concentrations (often in the nMol/L range) are controlled by the presence and photochemical properties (concerning Eu and probably U and Ag) of mainly biogenic organic matter (both DOC and POC, and DON). With chitin forming the outer hull of mobile organisms (animals), this biopolymer is expected to take part in metal distribution in aquatic (limnetic and riverine) ecosystems. Having studied the attachment of many different elements to both crayfish and grafted (marine shrimp) chitin, with the highest accumulations observed in Bi, V, Ni, and LREEs, one should consider secondary biochemical transformations which take place at different water and sediment levels. After chitin had been embedded into sediment, methanogenesis (which requires Ni), Bi, and Sb biomethylations and photodesorption in the illuminated water column will occur if there are appropriate organics, causing the vertical separation of Eu from other REEs, at least during the daytime. Eutrophication will enhance both the production and especially the photooxidation rates of organics in water because phosphorylated sugars and lipids are formed quantitatively within min P, which enter water and undergo Eu-mediated photooxidation much more readily. Another biopolymer, gelatin, acts as an inert matrix-enhancing organic photooxidation product via Eu, producing chemical waves, indicating autocatalysis upon light impact. From the redox-related photodesorption of metal analytes from chitin, both sensors and devices for (light-assisted) electrochemical energy conversion are being developed by our workgroup. The electrochemical determination of adsorption thermodynamics on chitin is thus directly linked to its applications in environmental monitoring and technology.
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