Comparaison de différents protocoles de spéciation séquentielle du phosphore dans des sédiments de rivière

Trois méthodes classiques de spéciation séquentielle du phosphore ont été appliquées aux sédiments de la rivière Sûre, à une sélection de ses affluents de taille variable, ainsi qu'aux sédiments du prébarrage Misère, un petit réservoir eutrophe situé sur la Sûre. Les protocoles comparés sont ceux de HIELTJES et LIJKLEMA (H et L), de PALUDAN et JENSEN (P et J) et de GOLTERMAN et BOOMAN (G et B).Le phosphore total des sédiments étudiés s'élève à 0,6 mg·P·g-1 séd. sec pour les petits sous-bassins expérimentaux (de l'ordre de 1 km2), à 0,8-1,0 mg·P·g-1 séd. sec pour les bassins de taille moyenne (20 à 320 km2) et à 1,8 mg·P·g-1 séd. sec pour le prébarrage Misère. Les schémas de (H et L) et de (P et J) reproduisent de façon similaire les différences qualitatives existant entre les sédiments. Toutefois les parts relatives des différentes fractions varient selon le protocole utilisé. Les rendements d'extraction obtenus avec le schéma de (G et B) sont sensiblement supérieurs aux deux autres méthodes et sont très liés aux teneurs en phosphore total des mêmes échantillons.Pour le P-labile, une bonne corrélation est obtenue entre les concentrations extraites selon les protocoles de (H et L) et (P et J) (R2 =0,84, P < 0,001) ; cependant les valeurs absolues sont 40 % supérieures pour le premier (H et L) qui utilise NH4Cl comme extractant au lieu de H2O. La fraction P- (Fe+Al) de (H et L) et la somme des fractions P-Fe et P-Al de (P et J) sont également bien corrélées (R2 =0,90, P < 0,001), mais avec des valeurs 30 % supérieures pour le second protocole (P et J) qui réalise l'extraction en deux étapes. La fraction P-Fe de (G et B) est moins bien corrélée à la fraction P-Fe de (P et J) (R2 =0,74, P < 0,01), et les résultats obtenus selon ces deux protocoles sont très éloignés en valeur absolue. Quant à la fraction P-Ca, les résultats du protocole de (G et B) ne sont ni corrélés ni similaires à ceux des deux autres schémas, en raison de la nature complètement différente des extractants appliqués.The Haute-Sûre river, with a rural watershed of 428 km2 is the principal entry of the Esch-sur-Sûre reservoir, which is mainly used for drinking-water supply. The role of particulate phosphorus (suspended matter and sediments) is important to maintain the trophic level of lakes, and in particular of reservoirs, often receiving higher external nutrient loads than natural lakes. Indeed, phosphorus flux in the Haute-Sûre basin occurs mainly in particulate form, closely linked to the hydrological and morphological conditions of its drainage basin. Several authors have shown that the fractionation of sedimentary phosphorus is strongly correlated with its bioavailability.This study was carried out in the framework of a larger project concerning the characterisation of the phosphorus from the sediments of the Sûre river watershed. The choice among the fractionation procedures described in literature and the comparison of the different results remains often difficult because of the different nature of the proposed extracting solutions, but also because of variable solid: liquid ratios, or the different exposure times proposed. Three traditional fractionation methods, HIELTJES and LIJKLEMA (H and L) (1980), PALUDAN and JENSEN (P and J) (1995) and GOLTERMAN and BOOMAN (G and B) (1988), were thus tested in the present study and applied to sediments from the Sûre river bed and a selection of its tributaries of variable size as well as to the Misère predam sediments, a small reservoir located upstream from the main reservoir.The first protocol (H and L) classes the sedimentary phosphorus in four fractions: labile-P obtained with a NO4C1 1M solution, (Fe+Al)-P with NaOH 0.1M as reagent, Ca-P with a HCl 0.5 M solution and residual-P obtained by difference of the three precedent fractions with total P. The second (P and J) separates sedimentary phosphorus in 6 fractions: labile-P extracted with H2O, Fe-P with a dithionite-bicarbonate solution (NaHCO3 0.11 M and Na2 S2 O4 0.11 M), Al-P with a NaOH 0.1 M solution after acidification of the supernatant to pH=1 and separation of the resultant precipitate, AH-P (humic acids - P) obtained after mineralisation (H2 SO4 /K2 SO4 sat. at 400°C) of the previous precipitate, Ca-P with a HCl 0.5 M solution, and finally residual-P after drying and mineralisation of the sediment having undergone all the previous steps (H2 SO4 /K2 SO4 sat. at 400°C). The third tested protocol (G and B) proposes chelates as extracting solutions: the fraction Fe-P with Ca-NTA/dithionite (CaCO3 0.04 M + NTA 0.02 M - Na2 S2 O4 0.045 M), and the Ca-P fraction with Na-EDTA 0.05 M at pH=8.The obtained results demonstrate a substantial difference between the sampled sediments. The total phosphorus content of the sampled sediments varied between 0.6 mg·P·g-1 dw for the small experimental basins (around 1 km2), 0.8 to 1.0 mg·P·g-1 dw for the medium-sized basins (20 to 320 km2) and 1.8 mg·P·g-1 dw for the Misère predam (lentic system). As regards the phosphorus fractionation, the (H and L) and the (P and J) procedures are concordant from the qualitative point of view, the relative importance of the different fractions varying nevertheless according to the used scheme. With the (G and B) method the extracted P fractions were highest. In relative terms (% P-fraction in relation to total-P), the sampled sediments have a very similar behaviour according to (G and B), the quantitative differences between samples being strongly correlated to their total phosphorus content.A good correlation was found between the labile-P fractions determined according to (H and L) and according to (P and J) (R2=0.84, P < 0.001) with however 40% higher values for (H and L). The P-(Fe+Al) fraction of (H and L) and the sum of the fractions P-Fe + P-Al of (P and J) are correlated as well (R2=0.90, P < 0.001) with 30% higher values for (P and J). Regarding the P-Fe fraction, the results obtained with the (G and B) and (P and J) protocols are correlated (R2=0.74, P < 0.01), but results are quantitatively quite different. The P-Ca fraction of the (G and B) protocol is badly correlated and very different from the two other procedures, because of the completely different nature of the extracting solutions

Comparative Study of Transport Processes of Nitrogen, Phosphorus, and Herbicides to Streams in Five Agricultural Basins, USA

Agricultural chemical transport to surface water and the linkage to other hydrological compartments, principally ground water, was investigated at five watersheds in semiarid to humid climatic settings. Chemical transport was affected by storm water runoff , soil drainage, irrigation, and how streams were linked to shallow ground water systems. Irrigation practices and timing of chemical use greatly affected nutrient and pesticide transport in the semiarid basins. Irrigation with imported water tended to increase ground water and chemical transport, whereas the use of locally pumped irrigation water may eliminate connections between streams and ground water, resulting in lower annual loads. Drainage pathways in humid environments are important because the loads may be transported in tile drains, or through varying combinations of ground water discharge, and overland flow. In most cases, overland flow contributed the greatest loads, but a significant portion of the annual load of nitrate and some pesticide degradates can be transported under base-flow conditions. The highest basin yields for nitrate were measured in a semiarid irrigated system that used imported water and in a stream dominated by tile drainage in a humid environment. Pesticide loads, as a percent of actual use (LAPU), showed the effects of climate and geohydrologic conditions. The LAPU values in the semiarid study basin in Washington were generally low because most of the load was transported in ground water discharge to the stream. When herbicides are applied during the rainy season in a semiarid setting, such as simazine in the California basin, LAPU values are similar to those in the Midwest basins