A systematic comparison of the diffusion coefficients of cations (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) and oxyanions (Al, As, Mo, Sb, V, W) in open (ODL) and restricted (RDL) diffusive layers used by the DGT technique was undertaken. Diffusion coefficients were measured using both the diffusion cell (Dcell) method at pH 4.00 and the DGT time-series (D(DGT)) method at pH 4.01 and 7.04 (pH 8.30 was used instead of 7.04 for Al) using the Chelex-Metsorb mixed binding layer. The performance of Chelex-Metsorb as a new DGT binding layer for Al uptake was also evaluated for the first time. Reasonable agreement was observed between D(cell) and D(DGT) measurements for both ODL and RDL, except for V and W. The ratios of D(cell)/D(DGT) for V of 0.44 and 0.39, and for W of 0.66 and 0.63 with ODL and RDL respectively, were much lower due to the formation of a high proportion of polyoxometalate species at the higher concentrations required with the D(cell) measurements. This is the first time that D values have been reported for several oxyanions using RDL. Except for Al at pH 8.30 with ODL, all D(DGT) measurements were retarded relative to diffusion coefficients in water (DW) for both diffusive hydrogels. Diffusion in RDL was further retarded compared with ODL, for all elements (0.66-0.78) with both methods. However, the degree of retardation observed changed for cations and anions at each pH. At pH 7.04 cations had a slightly higher D(DGT) and oxyanions had a slightly lower D(DGT) than at pH 4.01 for both ODL and RDL. It is proposed that this is due to partial formation of acrylic acid functional groups (pKa ≈4.5), which would be fully deprotonated at pH 7.04 (negative) and mostly protonated at pH 4.01 (neutral). As Al changes from being cationic at pH 4.01 to anionic at pH 8.30 the results were more complex.
Four different DGT binding layers were used to make selective measurements of trace metals in coastal waters within The Broadwater (Gold Coast, Queensland). Chelex and PAMPAA (polyacrylamide-polyacrylic acid) binding layers were used to measure cations (Cd, Co, Cu, Mn, Ni, Pb, Zn), and Metsorb was used to measure anions (Al, As, Mo, Sb, V, W). A mixed binding layer (MBL) containing both Chelex and Metsorb was used to measure each of the trace metals and determine diffusive boundary layer (DBL) thicknesses. DGT measurements that were not corrected for the DBL thickness (0.049-0.087) were underestimated by 70% on average. Good agreement was observed between DGT-MBL and DGT-Chelex for measurement of Cd, Co, Cu, Ni, Pb and Zn, and between DGT-MBL and DGT-Metsorb for As, Sb and V. DGT-MBL measured significantly higher concentrations for Mn (compared with DGT-Chelex) and Al (compared with DGT-Metsorb). DGT-Chelex measured only 6-8% of Al species measured by either DGT-MBL or DGT-Metsorb. DGT-PAMPAA measurements of Cu, Pb and Al were lower than those of either DGT-MBL or DGT-Chelex varying from 74-81% for Cu to 54-70% for Pb and 51-55% for anionic Al(OH)4(-), suggesting that this binding layer may make more selective measurements. All measured trace metal concentrations were well below ANZECC water quality guidelines, except for Cu which was 2 to 10 times higher than trigger values. Each of the DGT techniques was deployed using both open and restricted diffusive layers (ODL and RDL). Most trace metal measurements were not significantly different with ODL and RDL for all binding layers. However, concentrations of Cu (CRDL/CODL = 0.68-0.75) and Al (CRDL/CODL = 0.73-0.79) were significantly different with DGT-MBL, DGT-Chelex and DGT-Metsorb.
Some aspects of the reproductive biology of the Persian Tooth-carp Aphanius persicus, an endemic cyprinodontid fish species from Maharlu Lake basin, Fars province, southern Iran, were studied by regular monthly collections throughout one year. Significant differences were observed between the total number of females and males, females being more abundant. Based on the pattern of the gonado-somatic index and Dobriyal Index, it was concluded that this fish has a prolonged active reproductive period which is a type of adaptation by short-lived small fishes to environmental conditions. Very small fish having mature and hydrated eggs were observed, indicating early sexual maturation. The average egg diameter was 0.53 mm. The absolute and relative fecundity was 115.7 and 90.01 respectively and it was related to fish size (total length and total weight) and also to gonad weight.Kurzfassung. Im Rahmen von regelmäßigen Aufsammlungen über ein Jahr hinweg wurde die Fortpflanzungsbiologie des Persischen Zahnkärpflings, Aphanius persicus, im Becken des Maharlu-Sees in der Fars-Provinz im Südiran untersucht, der dort endemisch vorkommt. Im Geschlechtsverhältnis wurden signifikante Unterschiede gefunden, wobei Weibchen deutlich häufi-ger sind. Aus dem Muster des gonado-somatischen Index und des Dobriyal-Index wurde geschlossen, dass diese Art eine verlängerte Reproduktionsperiode besitzt, die als Anpassung der kurzlebigen und kleinen Art an Umweltbedingungen gedeutet werden kann. Sehr kleine Individuen wurden mit reifen und hydrierten Eiern beobachtet, was auf frühe sexuelle Reifung hinweist. Der durchschnittliche Durchmesser der Eier betrug 0.53 mm. Die absolute und relative Fruchtbarkeit betrug 115.7 bzw. 90.01 und war mit der Größe der Fische (Gesamtlänge und Gesamtgewicht) sowie dem Gonadengewicht korreliert.
The performance of DGT-Chelex, DGT-Metsorb and DGT-MBL (Chelex-Metsorb mixed binding layer) with open and restricted diffusive layers for trace metal (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) and oxyanion (As, Mo, Sb, V) measurements, was evaluated in four natural waters with different pH (range 3.29-7.81). In moderately acidic (pH ≈ 5) and circumneutral (pH ≈ 6.3) waters, all three binding layers measured relatively similar concentrations of Al, while in more alkaline waters (pH ≈ 8) DGT-MBL measured higher concentrations than the other two binding layers. The measurements of DGT-Chelex and DGT-MBL for Co, Cu, Ni, Pb and Zn, and DGT-Metsorb and DGT-MBL for As, Sb and V were within 82-119% and not statistically different (p > 0.05) over the pH range 5-8. Mn measurements by DGT-Chelex and DGT-MBL were quite similar (95%) at pH 6.3, while DGT-MBL measured higher concentrations than DGT-Chelex at other pHs. The ratios of measured concentrations with different diffusive layers (C/C) were between 0.78 and 1.12 for all binding layers and no statistical differences (p > 0.05) were observed, except for Al at pH 7.81 and Cu at pH 6.28. DGT-MBL was comparable to DGT-Chelex for the measurement of most trace metals, and to DGT-Metsorb for the measurement of most oxyanions, over the pH range 5.05-7.81. Overall, DGT-MBL is superior to the other tested binding layers because it can simultaneously measure cations and anions, and accurately measure dissolved Al, across the greatest range of environmental conditions.
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