Barium as a potential indicator of phosphorus in agricultural runoff.

In many catchments, anthropogenic input of contaminants, and in particular phosphorus (P), into surface water is a mixture of agricultural and sewage runoff. Knowledge about the relative contribution from each of these sources is vital for mitigation of major environmental problems such as eutrophication. In this study, we investigated whether the distribution of trace elements in surface waters can be used to trace the contamination source. Water from three groups of streams was investigated: streams influenced only by agricultural runoff, streams influenced mainly by sewage runoff, and reference streams. Samples were collected at different flow regimes and times of year and analyzed for 62 elements using ICP-MS. Our results show that there are significant differences between the anthropogenic sources affecting the streams in terms of total element composition and individual elements, indicating that the method has the potential to trace anthropogenic impact on surface waters. The elements that show significant differences between sources are strontium (p < 0.001), calcium (p < 0.004), potassium (p < 0.001), magnesium (p < 0.001), boron (p < 0.001), rhodium (p = 0.001), and barium (p < 0.001). According to this study, barium shows the greatest potential as a tracer for an individual source of anthropogenic input to surface waters. We observed a strong relationship between barium and total P in the investigated samples (R(2) = 0.78), which could potentially be used to apportion anthropogenic sources of P and thereby facilitate targeting of mitigation practices.

Diagenesis of settling seston: identity and transformations of organic phosphorus.

Solution (31)phosphorus NMR spectroscopy and sequential fractionation were used to follow diagenetic changes in phosphorus forms during decomposition of settling seston in Lake Nordborg, a shallow eutrophic lake in Denmark. In a decomposition experiment, seston released >60% of their total phosphorus during ~50 days incubation, although seston collected during summer contained more phosphorus and released it over a longer period compared to seston collected during spring. Seston decomposition increased concentrations of potentially bioavailable polyphosphate and phosphodiesters, but also promoted the formation of refractory phosphorus forms that might be buried permanently in the sediment. Combining these results with in situ measurements of phosphorus concentrations in lake water and sediment traps revealed that the release from settling seston plays only a minor role in the accumulation of phosphorus in the hypolimnion of Lake Nordborg.

Sediment phosphorus extractants for phosphorus-31 nuclear magnetic resonance analysis: a quantitative evaluation.

The influence of pre-extractant, extractant, and post-extractant on total extracted amounts of P and organic P compound groups measured with 31P nuclear magnetic resonance (31P-NMR) in lacustrine sediment was examined. The main extractants investigated were sodium hydroxide (NaOH) and sodium hydroxide ethylenediaminetetraacetic acid (NaOH-EDTA) with bicarbonate buffered dithionite (BD) or EDTA as pre-extractants. Post extractions were conducted using either NaOH or NaOH-EDTA, depending on the main extractant. Results showed that the most efficient combination of extractants for total P yield was NaOH with EDTA as pre-extractant, yielding almost 50% more than the second best procedure. The P compound groups varying the most between the different extraction procedures were polyphosphates and pyrophosphates. NaOH with BD as pre-extractant was the most efficient combination for these compound groups.

Effects of aluminum treatment on phosphorus, carbon, and nitrogen distribution in lake sediment: a 31P NMR study.

The effects of aluminum (Al) treatment on sediment composition of carbon (C), nitrogen (N) and phosphorus (P) were investigated in sediment representing pre- and post-treatment years in the Danish Lake Sønderby. 31P NMR spectroscopy analysis of EDTA-NaOH extracts revealed six functional P groups. Direct effects of the Al treatment were reflected in the orthophosphate profile revealing increased amounts of Al-P in the sediment layers representing the post-treatment period, as well as changes in organic P groups due to precipitation of phytoplankton and bacteria at the time of Al addition. Furthermore, changes in phytoplankton community structure and lowered production due to the Al treatment resulted in decreased concentrations of sediment organic P groups and total C. Exponential regressions were used to describe the diagenesis of C, N, and P in the sediment. From these regressions, half-life degradation times and C, N, and P burial rates were determined.

Biogenic phosphorus in oligotrophic mountain lake sediments: differences in composition measured with NMR spectroscopy.

Phosphorus (P) composition in alkaline sediment extracts from three Swedish oligotrophic mountain lakes was investigated using 31P-NMR spectroscopy. Surface sediments from one natural lake and two mature reservoirs, one of which has received nutrient additions over the last 3 years, were compared with respect to biogenic P composition. The results show significant differences in the occurrence of labile and biogenic P species in the sediments of the different systems. The P compound groups that varied most between these three systems were pyrophosphate and polyphosphates, compound groups known to play an important role in sediment P recycling. The content of these compound groups was lowest in the reservoirs and may indicate a coupling between anthropogenic disturbances (i.e., impoundment) to a water system and the availability of labile P species in the sediment. A statistical study was also conducted to determine the accuracy and reliability of using 31P-NMR spectroscopy for quantification of sediment P forms.

Sediment extraction and clean-up for organic phosphorus analysis by electrospray ionization tandem mass spectrometry.

A method to prepare NaOH sediment extracts for organic P compound analysis with electrospray ionization tandem mass spectrometry (ESI-MS-MS) was developed on natural samples. Ion exchange, rotary evaporation and mass cut-off filtering proved to be suitable for sample preparation. Samples were analyzed with ESI-MS-MS, and reproducibility and repeatability of the method was calculated. In addition, (31)P-nuclear magnetic resonance spectroscopy ((31)P NMR) was used to measure recovery of different P compound groups such as orthophosphate (Ortho-P), orthophosphate monoesters (Monoester-P), orthophosphate diesters (Diester-P) and pyrophosphates (Pyro-P). The developed sample preparation method resulted in an easy-to-spray liquid for the ESI-MS-MS instrumentation. The overall P recovery was 65% and (31)P NMR showed that Diester-P, possibly in the form of DNA, was apparently lost through the filtering step most likely due to their size. Variances in the total intensities of the MS scans (relative standard deviation (R.S.D.) 35-54%) were for about 50% due to repeated MS runs. Covariances of the peaks in the MS spectra were calculated to be for about 30% due to the sample preparation procedure. Finally, with the ESI-MS-MS approach, 11 peaks in the mass spectra were found likely to represent phosphate containing compounds.

Sediment depth attenuation of biogenic phosphorus compounds measured by 31P NMR.

Being a major cause of eutrophication and subsequent loss of water quality, the turnover of phosphorus (P) in lake sediments is in need of deeper understanding. A major part of the flux of P to eutrophic lake sediments is organically bound or of biogenic origin. This P is incorporated in a poorly described mixture of autochthonous and allochthonous sediment and forms the primary storage of P available for recycling to the water column, thus regulating lake trophic status. To identify and quantify biogenic sediment P and assess its lability, we analyzed sediment cores from Lake Erken, Sweden, using traditional P fractionation, and in parallel, NaOH extracts were analyzed using 31P NMR. The surface sediments contain orthophosphates (ortho-P) and pyrophosphates (pyro-P), as well as phosphate mono- and diesters. The first group of compounds to disappear with increased sediment depth is pyrophosphate, followed by a steady decline of the different ester compounds. Estimated half-life times of these compound groups are about 10 yr for pyrophosphate and 2 decades for mono- and diesters. Probably, these compounds will be mineralized to ortho-P and is thus potentially available for recycling to the water column, supporting further growth of phytoplankton. In conclusion, 31P NMR is a useful tool to asses the bioavailability of certain P compound groups, and the combination with traditional fractionation techniques makes quantification possible.