Charlotte Jørgensen

Occurrence of orthophosphate monoesters in lake sediments: significance of myo- and scyllo-inositol hexakisphosphate.

Orthophosphate monoesters often constitute a significant fraction of total phosphorus in lake sediments. The knowledge on the specific composition and recalcitrance of these compounds is however limited. The main aim was therefore to identify and quantify specific orthophosphate monoesters in sediment from 15 Danish lakes by solution (31)P NMR spectroscopy. The four most quantitatively important orthophosphate monoesters were myo-inositol hexakisphosphate (myo-IP(6)), scyllo-inositol hexakisphosphate (scyllo-IP(6)) α-glycerophosphate (α-GP) and β-glycerophosphate (β-GP). The compounds were identified in 9, 4, 8 and in all 15 lakes, respectively. In total these four components made up 46-100% of the orthophosphate monoester pool. The glycerophosphates (GPs) are most likely degradation products of phospholipids, created as an artifact by the alkaline extraction procedure used for (31)P NMR spectroscopy, while the inositol hexakisphosphates (IPs) are naturally occurring compounds. There was a significant positive correlation between myo-IP(6) and total aluminium in the sediment and a negative correlation between myo-IP(6) and lake water pH, suggesting that myo-IP(6) is stabilized in the sediment by adsorption at slightly acidic or neutral conditions. In three lakes, the depth distribution of the orthophosphate monoesters was investigated. The content of scyllo-IP(6) and myo-IP(6) was constant with sediment depth in two of the lakes while the content of myo-IP(6) decreased with depth in one of the lakes. In all cases the IPs seem to be preserved with sediment depth to a higher extent than the orthophosphate diesters and especially the GPs suggesting that IPs can be a sink for phosphorus in the lake ecosystem or at least delay P-recycling for years.

Speciation of Inositol Phosphates in Lake Sediments by Ion-Exchange Chromatography Coupled with Mass Spectrometry, Inductively Coupled Plasma Atomic Emission Spectroscopy, and 31P NMR Spectroscopy

A method for the detection and speciation of inositol phosphates (InsP(n)) in sediment samples was tested, utilizing oxalate-oxalic acid extraction followed by determination by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) using electrospray ionization (ESI) in negative mode. The chromatographic separation was carried out using water and ammonium bicarbonate as mobile phase in gradient mode. Data acquisition under MS/MS was attained by multiple reaction monitoring. The technique provided a sensitive and selective detection of InsP(n) in sediment samples. Several forms of InsP(n) in the oxalate-oxalic acid extracted sediment were identified. InsP6 was the dominating form constituting 0.250 mg P/g DW (dry weight); InsP5 and InsP4 constituted 0.045 and 0.014 mg P/g DW, respectively. The detection limit of the LC-ESI-MS/MS method was 0.03 μM InsP(n), which is superior to the currently used method for the identification of InsP(n), (31)P nuclear magnetic resonance spectroscopy ((31)P NMR). Additionally sample handling time was significantly reduced.

Phosphate adsorption to iron sludge from waterworks, ochre precipitation basins and commercial ferrihydrite at ambient freshwater phosphate concentrations

ABSTRACT Measures such as storm water ponds, constructed wetlands and buffer strips along streams are used to reduce diffuse phosphorus (P) loading to surface waters. These systems often retain particulate P well, whereas the retention of dissolved P is less efficient and might require addition of P adsorbents. In this study, we screened waterwork ochre sludge (WWS) originating from groundwater treatment and ochre sludge from ochre precipitation basins along streams for their applicability as P adsorbents at ambient P concentrations. We compared with a commercial ferric hydroxide (CFH 12™) for which adsorption properties is well described. The adsorption capacity of 9 products was measured over 24 h at different P concentrations (5–2000 µg L−1), a range that covers Danish drainage water and stormwater. WWS desorbed phosphate at concentrations below 50–200 µg P L−1 and should only be considered for use in systems with a constantly high load of dissolved P. High affinity combined with little or no desorption characterized the commercial product and the ochre sludge from the precipitation basins, rendering these useful for treating drainage water and storm water. The study underlines that waste products may act as potentially effective P adsorbers at environmentally relevant P levels.

Nitrogen and Phosphorus Removal from Agricultural Runoff in Integrated Buffer Zones

Integrated buffer zones (IBZs) represent a novel form of edge-of-field technology in Northwest Europe. Contrary to the common riparian buffer strips, IBZs collect tile drainage water from agricultural fields by combining a ditch-like pond (POND), where soil particles can settle, and a flow-through filter bed (FILTERBED) planted with Alnus glutinosa (L.), a European alder (black alder). The first experimental IBZ facility was constructed and thoroughly tested in Denmark for its capability to retain various nitrogen (N) and phosphorus (P) species within the first three years after construction. We calculated the water and nutrient budget for the total IBZ and for the two compartments, POND and FILTERBED, separately. Furthermore, a tracer experiment using sodium bromide was conducted in order to trace the water flow and estimate the hydraulic residence time in the FILTERBEDs. The monthly average removal efficiency amounted to 10-67% for total N and 31-69% for total P, with performance being highest during the warm season. Accordingly, we suggest that IBZs may be a valuable modification of dry buffer strips in order to mitigate the adverse impacts of high nutrient loading from agricultural fields on the aquatic environment.