Spectrophotometric pH measurement in estuaries using thymol blue and m-cresol purple

The conditional acid dissociation constants (pK_a′) of two sulfonephthalein dyes, thymol blue (TB) and m-cresol purple (mCP), were assessed throughout the estuarine salinity range (0<S<40) using a tris/tris–HCl buffer and spectrophotometric measurement. The salinity dependence of the pK_a′ of both dyes was fitted to the equations (25 °C, total proton pH scale, mol kg soln⁻¹):

The estimated accuracy of pH measurements using these calculated pK_a′ values is considered to be comparable to that possible with careful use of a glass electrode (±0.01 pH unit) but spectrophotometric measurements in an estuary have the significant advantage that it is not necessary to calibrate an electrode at different salinities. pH was measured in an estuary over a tidal cycle with a precision of ±0.0005 pH unit at high (S>30) salinity, and ±0.002 pH unit at low (S<5) salinity. The pH increased rapidly in the lower salinity ranges (0<S<15) but less rapidly at higher salinities.     

Spectrophotometric determination of pH in seawater off Taiaroa Head,Otago, New Zealand: Full-spectrum modelling and prediction of pCO2 levels

Accurate measurement of seawater pH has long been sought by marine chemists (for example: [Dickson, A.G. 1993a. The measurement of sea water pH. Marine Chemistry, 44, 131–142, Dickson, A.G. 1993b. pH buffers for sea water media based on the total hydrogen ion concentration scale. Deep-Sea Research, 40, 107–118; Zhang, 1996; Tapp, M., Hunter, K.A., Currie, K. and Macaskill, B. 2000. Apparatus of continuous-flow underway spectrophotometric measurement of surface water pH. Marine Chemistry 72(2–4), 193–202; Friis, K., Koetzinger, A., Wallace, D.W.R. 2004. Spectrophotometric pH measurement in the ocean: Requirements, design and testing of an autonomous charge-coupled device detector system. Limnology and Oceanography: Methods 2, 126–136]. Recently, such attempts have taken on greater significance as anthropogenic carbon dioxide emissions may create rapidly changing oceanic pH. Spectrophotometric techniques have been accepted generally as the best for determination of seawater pH. Here we report a new technique using thymol blue as the indicator dye and fitting the entire spectrum from 400 to 900 nm rather than measuring the absorbance values at only two or three points in the spectrum. This full-spectrum modelling enables a reduction in signal to noise over other techniques. In the laboratory, we find with seawater samples a pH precision increase of five-fold “within” a sample and seven-fold “between” samples when comparing the full spectrum to the three-point method of analysis [Zhang, H., Byrne, R.H. 1996. Spectrophotometric pH measurements of surface seawater at in-situ conditions: absorbance and protonation behaviour of thymol blue. Marine Chemistry 52, 17–25].     

Responses of resident marsh fishes to stages ofPhragmites australis invasion in three mid Atlantic estuaries

Modification of brackish marshes by nonindigenousPhragmites australis has occurred across a broad geographical area in eastern North America. Among its effects on marsh processes,Phragmites may be increasingly unfavorable to marsh surface fishes as its invasion progresses within an estuary. We assessed the effect of thePhragmites invasion on resident marsh surface fishes by examining the population response ofFundulus heteroclitus (mummichog, 5–48 mm TL) andF. luciae (spotfin killifish, 5–41 mm TL) to four distinct invasion stages in three estuaries of the U.S. mid Atlantic region (New Jersey, Delaware, and Maryland). We documented precipitous declines in mean catch per unit effort ofF. heteroclitus in pit traps from natural marsh (51.6), through initial (33.8), early (12.3), and late invasion stages (2.4) across all sites. A similar pattern was documented forF. luciae, with mean catch per unit effort in pit traps declining from natural marsh (48.9), through initial (39.1), early (9.3), and late invasion stages (2.7). Population structure of both species also changed somewhat across invasion stages such that we collected a narrower size range of individuals of both species from late invasion stages. Patterns suggest that as thePhragmites invasion progresses, there is a decline in habitat function for larval and juvenileF. heteroclitus and an increased risk of extirpation ofF. luciae from brackish marshes along the east coast of the U.S.     

Uranium co-precipitation with iron oxide minerals

In oxidizing environments, the toxic and radioactive element uranium (U) is most soluble and mobile in the hexavalent oxidation state. Sorption of U(VI) on Fe-oxides minerals (such as hematite [α-Fe₂O₃] and goethite [α-FeOOH]) and occlusion of U(VI) by Fe-oxide coatings are processes that can retard U transport in environments. In aged U-contaminated geologic materials, the transport and the biological availability of U toward reduction may be limited by coprecipitation with Fe-oxide minerals. These processes also affect the biological availability of U(VI) species toward reduction and precipitation as the less soluble U(IV) species by metal-reducing bacteria.To examine the dynamics of interactions between U(VI) and Fe oxides during crystallization, Fe-oxide phases (containing 0.5 to 5.4 mol% U/(U + Fe)) were synthesized by means of solutions of U(VI) and Fe(III). Wet chemical (digestions and chemical extractions) and spectroscopic techniques were used to characterize the synthesized Fe oxide coprecipitates after rinsing in deionized water. Leaching the high mol% U solids with concentrated carbonate solution (for sorbed and solid-phase U(VI) species) typically removed most of the U, leaving, on average, about 0.6 mol% U. Oxalate leaching of solids with low mol% U contents (about 1 mol% U or less) indicated that almost all of the Fe in these solids was crystalline and that most of the U was associated with these crystalline Fe oxides. X-ray diffraction and Fourier-transform infrared (FT-IR) spectroscopic studies indicate that hematite formation is preferred over that of goethite when the amount of U in the Fe-oxides exceeds 1 mol% U (∼4 wt% U). FT-IR and room temperature continuous wave luminescence spectroscopic studies with unleached U/Fe solids indicate a relationship between the mol% U in the Fe oxide and the intensity or existence of the spectra features that can be assigned to UO₂²⁺ species (such as the IR asymmetric υ₃ stretch for O = U = O for uranyl). These spectral features were undetectable in carbonate- or oxalate-leached solids, suggesting solid phase and sorbed U(VI)O₂²⁺ species are extracted by the leach solutions. Uranium L₃-edge x-ray absorption spectroscopic (XAFS) analyses of the unleached U-Fe oxide solids with less than 1 mol% U reveal that U(VI) exists with four O atoms at radial distances of 2.19 and 2.36 Å and second shell Fe at a radial distance at 3.19 Å.Because of the large ionic radius of UO₂²⁺ (∼1.8 Å) relative to that of Fe³⁺ (0.65 Å), the UO₂²⁺ ion is unlikely to be incorporated in the place of Fe in Fe(III)-oxide structures. Solid-phase U(VI) can exist as the uranyl [U(VI)O₂²⁺] species with two axial U-O double bonds and four or more equatorial U-O bonds or as the uranate species (such as γ-UO₃) without axial U-O bonds. Our findings indicate U⁶⁺ (with ionic radii of 0.72 to 0.8 Å, depending on the coordination environment) is incorporated in the Fe oxides as uranate (without axial O atoms) until a point of saturation is reached. Beyond this excess in U concentration, precipitating U(VI) forms discrete crystalline uranyl phases that resemble the uranyl oxide hydrate schoepite [UO₂(OH)₂·2H₂O]. Molecular modeling studies reveal that U⁶⁺ species could bond with O atoms from distorted Fe octahedra in the hematite structure with an environment that is consistent with the results of the XAFS. The results provide compelling evidence of U incorporation within the hematite structure.