Earth and Planetary Science Letters 210 (2003) 249^258 www.elsevier.com/locate/epsl Tracing the source of sediment and phosphorus into the Great Barrier Reef lagoon Malcolm McCulloch a; , Christine Pailles b;1 , Philip Moody b , Candace E. Martin a;2 b a Research School of Earth Sciences, Australian National University, Canberra, ACT 0200, Australia Department of Natural Resources and Mines, Natural Resource Sciences, 80 Meiers Road, Indooroopilly, QLD 4068, Australia Received 18 July 2002; received in revised form 24 January 2003; accepted 14 March 2003 Abstract Neodymium and strontium isotopic systematics show that terrestrial phosphorus (P) entering the inner Great Barrier Reef (GBR) is dominated by the transport and dispersal of fine-grained basaltic soils. Soils derived from alkali basalts have high total P (3000^4000 mg/kg) and distinctive 143 Nd/144 Nd isotopic signatures (ONd V+3 to +5), while the more common Palaeozoic granitic/metamorphic soils have much lower total P (300^600 mg/kg) and 143 Nd isotopic signatures (ONd V38). The nearshore environment ( 6 5 km from the coast) is dominated by coarse-grained, graniticderived fluvial detritus, while s 20 km from the coast, carbonate-rich sediments with increasing contributions from basaltic components become more important. In the offshore sites adjacent to coral reefs, it is shown that basaltderived sediments can account for s 90% of the terrestrial P, although making up less than half of the total terrigenous detritus. Equilibrium phosphorus concentration measurements on the marine sediments indicate that P enters the GBR lagoon via a two-stage process. Firstly, during episodic flood events, P is transported into the GBR lagoon on P-retentive fine-grained suspended sediments, with only minor desorption of P occurring in the low-salinity flood plumes. Desorption of P mainly occurs over longer timescales, predominantly in regions of sediment anoxia, with release of PO33 4 directly into marine pore waters probably via reduction of ferric phosphates, and subsequent release into the water column by re-suspension. This process causes P depletion of the re-deposited sediments. = 2003 Elsevier Science B.V. All rights reserved. Keywords: sediment phosphorus tracing; Great Barrier Reef; degradation; neodymium^strontium isotopes 1. Introduction * Corresponding author. E-mail address: malcolm.mcculloch@anu.edu.au (M. McCulloch). 1 Present address: C.E.R.E.G.E., Europole Mediterraneen de l’Arbois, BP 80, 13545 Aix-en-Provence Cedex, France. 2 Present address: Geology Department, University of Otago, Dunedin, New Zealand. Enhanced levels of nutrients and sediment are one of the major causes of coral reef degradation. The reasons are complex and incompletely understood, but it is clear that enhanced nutrient loads from erosion of agricultural land [1^4], acting together with climatic stresses, such as cyclones and unusually high ocean temperatures [3,5], are prov- 0012-821X / 03 / $ ^ see front matter = 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0012-821X(03)00145-6 EPSL 6623 22-4-03 Cyaan Magenta Geel Zwart 250 M. McCulloch et al. / Earth and Planetary Science Letters 210 (2003) 249^258 ing to be a lethal combination. Furthermore, the regeneration of coral reefs following extreme climatic events, such as the 1997^98 coral mass bleaching [3,5^7], is often being inhibited due to algal blooms and eutrophication from high nutrient loads in the water column. Determining the source and pathways through which anthropogenically derived sediments and nutrients enter coral reefs is thus an essential prerequisite for ensuring their long-term sustainability. The Great Barrier Reef (GBR) is a complex assemblage of barrier, patch, platform and fringing reefs, extending for over 2000 km along the northeastern coastline of Australia. Although large sections are distal from direct terrestrial in£uences, inshore parts, especially in the central and northern GBR, are impacted by runo¡ from large rivers. The river £ows are generally highly episodic, being associated with cyclones or occasionally intense monsoonal depressions. During these high-intensity events there can be massive discharges of freshwater and suspended sediments into the nearshore GBR lagoon. For example, during the Cyclone Sadie £ood event of 1994, both the volume of water discharged and the suspended loads of the Johnstone River increased by approximately two orders of magnitude [8]. The river £ow increased from an average rate of V60 m3 /s to 6000 m3 /s with the suspended load increasing from V6 mg/l to 220^550 mg/l [9,10]. As a consequence, large, low-salinity, high-turbidity £ood plumes were discharged into the inner GBR lagoon. Depending on hydrodynamic conditions [11,12] such plumes generally persist for at least several weeks and occasionally for several months as they are advected northwards along the coast. In order to constrain the provenance of phosphorus £uxes that are entering the inshore region of the GBR lagoon, we have determined P concentrations and Nd^Sr isotopic compositions of terrestrially derived sediments from the Johnstone River £ood plume and from bottom sediments in a transect to the reef. The Johnstone River drains a medium-sized catchment of 1634 km2 . Catchment geology comprises Palaeozoic granitic and metamorphic rocks, overlain by the Tertiary, Atherton basalts [13] (Fig. 1). Most of the agri- culture (sugar, banana plantations and tropical fruits) is restricted to the basaltic provinces where fertile ferrosol soils have developed. These soils have excellent drainage characteristics, are well structured and have high retention capacities for the important nutrient element phosphorus [14]. Leaching of P in soluble form is thus usually minimal, but soil loss into rivers may occur from stream-banks and cultivated slopes during highintensity rainfall events[14^17]. Basaltic soils typically have high indigenous contents of P (3000^ 4000 mg/kg), which together with their large proportion of ¢ne clay-size particles makes them a potentially important source of P for the nearshore GBR. 2. Methods Systematic sampling of bottom sediments [16^ 18] was undertaken along both the Johnstone and South Johnstone rivers, the estuary and from two VE^W marine transects from the river mouth to the Gibson and Howie reefs in the central GBR (Fig. 1). Marine samples located at a depth of 6 25 m were collected by SCUBA divers, with all other samples (river sediments and o¡shore samples at s 25 m depth) being collected using a Van Veen grab sampler capable of recovering an undisturbed sample of the upper 10 cm of bottom sediment. Plume sediment samples were collected in February 1994 in the Johnstone River estuary following Cyclone Sadie. Grab and plume samples were immediately frozen at 320‡C until analysis. Phosphorus was separated into organic and inorganic P using 20% HCl with total P being estimated by the sum of these two fractions using procedures described in [19]. Surface soil samples were also obtained from the Berner Creek, a headwater catchment of the North Johnstone River. This catchment was chosen as it is dominated by basaltic soils and has regions where phosphate fertilisers have been applied. For Nd^Sr isotopic analyses 50^100 mg samples were dissolved in Te£on bombs using a mixture of nitric and HF acids and separated using cation exchange columns. Prior to this, marine samples were subjected to a leaching by acetic EPSL 6623 22-4-03 Cyaan Magenta Geel Zwart M. McCulloch et al. / Earth and Planetary Science Letters 210 (2003) 249^258 251 Fig. 1. Map showing the distribution of the main geologic units [13] in the Johnstone River catchment and location of coral reefs. Soils developed on Tertiary basalts are an important constituent of both the North and South Johnstone River sub-catchments. Solid symbols show locations of marine sediment samples. acid to remove any carbonate component. Nd and Sr isotopic compositions were determined on a Finnigan MAT 261 thermal ionisation mass spectrometer. Usual within-run precisions of better than R 0.00002 were obtained on 87 Sr/ 86 Sr and 143 Nd/144 Nd ratios. Sr ratios are normalised to 86 Sr/88 Sr = 0.1194 and Nd ratios to 146 Nd/ 144 Nd = 0.7219. The NBS 987 standard gave an average of 87 Sr/86 Sr = 0.71020 R 2 (2c, n = 8) and the nNd-1 inhouse standard 143 Nd/144 Nd = 0.512188 R 7 (2c, n = 7). 143 Nd/144 Nd ratios are reported as ONd values with ONd = [(143 Nd/ 144 Ndsample )/(0.51265)31]U104 . 3. Results 3.1. Phosphorus and Nd elemental abundances Within the Johnstone River, sediments have total P ranging from 400 to 800 mg/kg (Fig. 2) with the inorganic fraction generally making up more than 75% of the Ptot [16]. The organic component of P (Table 1) was most important in the estuarine sediments, where it contributed up to 50% of the Ptot [16]. Tributaries (not shown in Fig. 1) have even higher Ptot , approaching those of the basalt-derived soils (Ptot V2000^4000 mg/kg). No EPSL 6623 22-4-03 Cyaan Magenta Geel Zwart 252 M. McCulloch et al. / Earth and Planetary Science Letters 210 (2003) 249^258 di¡erences were observed in the Ptot levels for basalt-derived soils that had been subjected to phosphate fertilisers compared to unfertilised soils (Table 1). This is consistent with the high indigenous contents of P in basaltic soils. On the GBR inner shelf, within 5 km of the coast, the Ptot ranged from 110 to 200 mg/kg with the sediments being dominated by coarse £uvial sands ( 6 10% silt+clay) [18]. From 5 to 12 km, the sediments consisted of anoxic mud (80% silt+clay) with Ptot ranging from V250 to 330 mg/kg (Fig. 2). From 12 to 30 km the amount of CaCO3 (mainly skeletal debris) increased signi¢cantly with a corresponding decrease in the silt+clay fraction ( 6 10% at s 20 km). Despite dramatic changes in the sedimentology, especially decreasing amounts of silt and clay, Ptot remained almost constant at V250^300 mg/kg. These levels of Ptot are similar to those previously obtained for GBR reef sediments [20,21] and much lower than the values in the suspended loads carried in £ood plumes (Ptot V1900 mg/kg). The relatively uni- form levels of P within the sediments of the inner GBR lagoon may result from mixing by acrossreef dispersal processes [22,23] and/or approximately equal proportions of P coming from marine versus terrestrial sources. The Nd elemental abundances are shown in Fig. 2. The lowest concentrations (Nd 6 10 ppm) are present in the quartz/feldspar £uvial sands close to the river mouth and highest concentrations (NdV40 ppm) in the clay^silt-dominated anoxic zone 5^12 km o¡shore. An unexpected observation is that in the more distal carbonate-rich sediments (20^32 km o¡shore) the Nd concentrations remain nearly constant at moderate levels (8^14 ppm), that is 1/3 to 1/2 of typical continental abundances [24,25], despite increasing percentages of CaCO3 . Since Nd is almost exclusively derived from terrestrial sources (abundances in marine carbonates and seawater are U1033 ^ U1036 lower than average continental crust) this indicates the presence of a widely distributed terrestrially derived clay component that makes up 20^30% of the total carbonate-rich sediments. 3.2. Nd^Sr isotopic constraints on sediment provenances Fig. 2. Total P (inorganic+organic) in sediments from the Johnstone River, estuary [18] and o¡shore transects, plotted versus distance from the Johnstone River mouth. Suspended river sediments (open circles) have the highest Ptot (800^2000 mg/kg) re£ecting the importance of ¢ne-grained high-P basaltic soils. The o¡shore bottom sediments (solid circles) have signi¢cantly lower Ptot (V300 mg/kg) than either the riverbottom or river-bank sediments (Ptot V800 mg/kg) or suspended £ood-plume sediments (Ptot V1900 mg/kg), indicating large-scale ( s 80%) P desorption in the marine bottom sediments. Nd concentrations in the marine sediments show that the highest Nd concentrations occur in the nearshore anoxic muds. Nd concentrations are also relatively high in the carbonate-rich reefal sediments, indicating the presence (V30%) of widely distributed ¢ne-grained terrestrial clays. To further constrain the provenance of the sediments and hence particulate-bound phosphorus that is entering the GBR lagoon, Nd^Sr isotopic analyses have been undertaken (Fig. 3) on the marine sediments, suspended sediments from a £ood plume and the range of soil types within the Johnstone River catchment. Neodymium is a particularly powerful isotopic tracer [24,25] as distinctive isotopic terrestrial signatures are preserved through the recent geochemical cycle of soil production, sediment transport and redeposition in the coastal environment. The Johnstone River catchment consists of isotopically contrasting rock types (Table 1), Tertiary basalts with relatively high 143 Nd/144 Nd (ONd V+3 to +5) [26] compared to more evolved Palaeozoic granites and metamorphics (ONd V37 to 39). Along the VE^W transect into the GBR, the ONd values increase progressively (i.e. to less negative values) from ONd = 38 to 34.5. The most rapid change is within the ¢rst 5 km of the coast, which is dom- EPSL 6623 22-4-03 Cyaan Magenta Geel Zwart M. McCulloch et al. / Earth and Planetary Science Letters 210 (2003) 249^258 253 Table 1 Isotopic and elemental data for the Johnstone River and Great Barrier Reef sediments Sample GBR sediments [18] GG 9984 W G (acetic) FF 9983 W F EE CC 9980 W C AA 9978 W J BB 9979 W II 9985 W B KK 9987 W LL Cyclone Sadie [17] Sadie SJ Sadie NJ Estuary sediments [16] Bay 10010 W Coccoo 10008 W Rocky Soils Metamorphic Tully Met 0^10 cm Tully Met 20^30 cm Granitic Tully Gr 0^10 cm Tully Gr 20^30 cm Basaltic Innisfail Bas 0^10 cm Innisfail.Bas 20^30 cm Berner Creek soils IL950011/1 IL950012/1 IL95030 fert IL95007/1 fert IL95007/7 fert IL95015 unfert IL95021 unfert IL95023 unfert Basalts [26] ath12 rr225 bk112 bk114 Distance (km) ONd 87 Sr/86 Sr Nd (ppm) 8.9 32 32 29 29 24 18 18 13 11 10 6 5 3 2 34.6 R 0.5 35.1 R 0.2 35.2 R 0.2 34.9 R 0.3 35.3 R 0.2 35.0 R 0.5 36.0 R 0.2 36.1 R 0.2 36.3 R 0.2 36.3 R 0.4 36.5 R 0.2 36.9 R 0.2 38.1 R 0.4 37.9 R 0.3 0.71447 R 1 0.71129 R 5 0.71806 R 2 0.70973 R 1 0.71127 R 1 0.71810 R 1 0.71653 R 2 0.71504 R 2 0.71527 R 1 0.71549 R 1 0.71900 R 6 0.71665 R 1 0.72077 R 1 0.72020 R 1 31.0 35.6 R 0.4 33.4 R 0.3 0.71816 R 1 0.71496 R 9 30.6 31.4 32.5 37.1 R 0.3 37.2 R 0.4 36.5 R 0.3 0.71922 R 2 0.72067 R 3 0.71544 R 1 36.4 R 0.3 0.71378 R 2 0.71705 R 1 14.2 14.1 40.4 32.0 Porganic (ppm) Ptotal (ppm) 67.5 79 61 55 39 34 39 14 24.5 17.5 2.5 14 0.3 0.3 18 328 49 9.5 298 260 31 235 35 287 77 334 1.5 0.5 8.3 1.2 0.98 37.7 R 0.3 38.0 R 0.4 0.82493 R 3 0.83519 R 2 18.9 14.0 0.2 R 0.4 0.0 R 0.2 0.70738 R 3 0.70779 R 5 12.9 2.4 R 0.3 3.9 R 0.3 4.7 R 0.3 3.6 R 0.3 3.3 R 0.3 2.8 R 0.3 4.1 R 0.3 3.5 R 0.3 0.70630 R 2 0.70455 R 2 0.70549 R 2 0.70598 R 2 0.70690 R 2 0.70513 R 2 0.70556 R 2 0.70552 R 2 5.2 R 0.3 3.4 R 0.3 3.0 R 0.3 5.8 R 0.3 0.70391 R 2 0.70461 R 2 0.70472 R 2 0.70367 R 2 inated by coarser £uvial sediments, presumably derived mainly from the granitic soils. The ONd values then increase steadily with distance o¡shore, from ONd = 36.5 to 34.5 in the carbon- CaCO3 (%) 440 290 1200 760 13.5 4080 2100 3893 4759 4080 2343 1979 1615 4241 4248 22.3 25.2 25.4 22 2760 1970 2260 4080 ate-dominated reef sediments. The trend towards less negative values with increasing distance from shore implies larger proportions of sediment derived from basaltic soils. This is consistent with EPSL 6623 22-4-03 Cyaan Magenta Geel Zwart 254 M. McCulloch et al. / Earth and Planetary Science Letters 210 (2003) 249^258 Fig. 3. Plot of the Nd isotopic composition of marine bottom sediments (solid), estuarine sediments (open), and suspended sediments collected from the North (NJ) and South (SJ) Johnstone rivers during the 1994 Cyclone Sadie. The systematic increase in ONd values with distance o¡shore indicates an increasing proportion of ¢ne-grained basaltic-derived soils. The proportion of basaltic relative to granitic soils is calculated assuming linear mixing with 40% by mass of basalt soil (ONd V3 R 1) contributing s 80% of the terrigenous derived P near the coral reefs (30^35 km). Within V5 km of the river mouth, sediments consist mainly of coarse-grained £uvial sediments of granitic origin and hence have more negative ONd values similar to their granitic parents (ONd V 38 R 1). (87 Sr/86 SrV0.705 R 0.001) compared to the parent basalt (87 Sr/86 SrV0.7040 R 0.0005), possibly indicating a small marine cyclic salt and/or aeolian contribution. Soils derived from the Palaeozoic granites, however, have very distinctive isotopic values, with ONd = 38 R 1 and 87 Sr/86 SrV0.82. The Sr isotopic composition of the granitic soil is likely to be highly variable, as high Rb/Sr phases such as mica have much higher 87 Sr/86 Sr ratios than the low Rb/Sr Ca-feldspars. For this reason the granitic soils would be expected to have a broad range of grain size-dependent 87 Sr/ 86 Sr ratios. An additional complication is that, in contrast to Nd, appreciable amounts of Sr are present in marine CaCO3 sediments with seawater 87 Sr/86 SrV0.7092. Although the carbonate component was largely removed from the sediments by leaching with acetic acid, small residues would shift the Sr isotopic composition to seawater ratios (Fig. 4). Assuming either linear or curvilinear mixing (Fig. 4) gives mass fractions of basaltic relative to granitic soils of V10 R 5% for sediments in the estuary and nearshore £uvial zone, increasing to V40 R 10% for the marine sediments nearest to observations that the basalt-derived soils are ¢ner-grained, having high clay contents (60^80%), and that once discharged into the inshore region of the GBR, prevailing hydrodynamic conditions allow only the ¢ner particles to be transported o¡shore. Deposition of coarser £uvial sands is generally restricted to the estuary and nearshore areas [22,23]. In order to better quantify the proportions of basalt- versus granite-derived soils entering the GBR, mixing relationships have been examined using combined Nd^Sr isotopic systematics. Basaltic soils from Berner Creek, a headwater catchment, have ONd = +2 to +5, a range which is very similar to their parent Tertiary basalts (Fig. 4). The fertilised soils do not show any shifts in ONd indicative of fertiliser addition [25]. Two size fractions from a basalt soil collected from the Johnstone River bank near Innisfail have ONd = +0.0 and 0.2. Strontium isotopic compositions of the soils tend to be shifted to slightly higher values Fig. 4. Mixing relationships for Nd^Sr isotopic systematics in sediments and end-member components. The marine sediments are modelled as representing mixtures of soils derived from Tertiary basalts [26] (ONd V3 R 1 and 87 Sr/86 SrV0.7055) and Palaeozoic granites and metamorphics (ONd V38 R 1 and 87 Sr/86 SrV0.72^0.82). Two bulk mixing curves are shown with (Sr/Nd)basalt soil /(Sr/Nd)granitic soil ranging from 1 (linear) to 20 (hyperbola), which give similar mass fractions of basalt. The near-reef sediments (25^35 km) have lower than anticipated 87 Sr/86 Sr, which may re£ect small amounts of residual marine carbonate having seawater 87 Sr/86 Sr (0.7092). EPSL 6623 22-4-03 Cyaan Magenta Geel Zwart M. McCulloch et al. / Earth and Planetary Science Letters 210 (2003) 249^258 255 Fig. 5. Schematic diagram showing the transport of suspended sediments and P predominantly as particulate form into the GBR lagoon. The release of P probably occurs as a consequence of iron reduction in anaerobic zones in the sea-£oor environment [27^29]. In the carbonate-rich sediments adjacent to the coral reefs, the Nd isotopic constraints indicate that V40% of the terrigenous sediment is derived from basalt soils. This implies that s 80% of terrestrial P entering the GBR is possibly derived from erosion of basaltic soils. the Gibson and Howie coral reefs (Fig. 1). Uncertainties in the mass fractions re£ect those in the Nd and Sr concentrations and isotopic compositions of the respective end-member components. Thus granitic detritus is the dominant sedimentary component, consistent with the observations that the main river channels are cut into granitic bedrock, and where present, the Tertiary basalts form only thin cappings [13,26]. Suspended sediments collected during the 1994 Cyclone Sadie [17] (Figs. 3 and 4) have Nd^Sr compositions that are either similar to the nearshore marine sediments (i.e. South Johnstone ONd = 35.6) or have slightly higher values (i.e. North Johnstone River ONd = 33.6), implying a greater proportion of basalt soil component (V50 R 10%) in the latter. Using the measured Ptot in the North Johnstone Sadie-suspended sediment (1900 mg/kg), together with P in basaltic (V3500 mg/kg) and granitic soils (600 mg/kg), also indicates approximately equal proportions of basalt versus granitic soils of 50 R 10% in the North Johnstone Sadie sample. This compares with V25% of basaltic soil in the South Johnstone suspended sediment. Interestingly, the average of the ONd values for the North and South Johnstone Cyclone Sadie soils is indistinguishable from the ONd composition of the most distal o¡shore sediments. This provides further con¢rmation that it is the ¢ne-grained suspended sediments that are transported more e⁄ciently o¡shore and northwards with the prevailing currents and winds. The presence of additional small contributions of terrigenous components from either more southerly river plumes such as from the Tully, Herbert and Burdekin rivers or possibly minor contributions from distal volcanic sources such as the Indonesian island-arc cannot be excluded, but in this study are not apparent. 4. Discussion and conclusions From the combined P^Nd^Sr systematics and EPSL 6623 22-4-03 Cyaan Magenta Geel Zwart 256 M. McCulloch et al. / Earth and Planetary Science Letters 210 (2003) 249^258 sedimentological constraints, a relatively coherent model can now be developed for the transport of terrestrial P into the GBR lagoon (Fig. 5). Basaltic soils make up 10^40% of the terrigenous sediment component deposited in the GBR from the Johnstone River catchment, with the proportion increasing with distance o¡shore (Fig. 3). However, in terms of overall P budgets, the basaltic soil is by far the most important component, accounting for up to 80^90% of the total terrestrialderived P reaching the coral reefs of the GBR. Assuming approximately equal contributions of P from terrestrial and marine sources this indicates that basalt-derived P may account for up to V40^50% of the total P incorporated in the coral reef sediments. The dominant mechanism for transport of terrestrial P into the nearshore environment of the GBR is via particulates, with £uvial-suspended sediments typically accounting for s 80% of total P (Ptot ) budget in £uvial systems [8]. There is no evidence for large-scale desorption of P from suspended sediments during transport into the marine environment. For example, equilibrium P concentration experiments [15, 17] conducted on suspended sediments ( s 0.45 Wm) collected in the Johnstone River estuary 5 days after £ooding associated with the 1994 Cyclone Sadie have been shown to have desorbed little or no P ( 6 1% of total P) when suspended in P-free water. Suspension of the same sediment in 3.5% NaCl (similar conductivity to seawater) indicated that salinity did not promote further P desorption. This suggests that as the £ood plume moves o¡shore, P is likely to undergo only limited desorption from suspended particulates, despite encountering increasing salinity [8,15^17]. Direct measurements of dissolved inorganic and organic P from the GBR £ood plumes [31] generally show the most elevated concentrations in the lowest-salinity portions ( 6 V2.5% NaCl) of £ood plumes. This suggests that, although the P budget in £ood plumes is generally dominated by particulate P, on shorter timescales direct input by rivers of nutrients (P and N) in dissolved form is still important [8,31]. These dissolved nutrients often result in enhanced productivity in the frontal convergence zone of £ood plumes, with rapid biological uptake and recycling of nutrients by phytoplankton [31]. Close to the estuary, £uvial sediments dominate [22,23], but in a zone 5^12 km o¡shore, ¢negrained anoxic muds (clay contents of 60^80%) predominate, with P an order of magnitude lower than that measured in the suspended plume sediments. This indicates that desorption of P occurs in the bottom sediments (Fig. 4), probably via the reduction of ferric phosphates [27^29]. On longer timescales phosphorus is thus mainly solubilised through the diagenesis of bottom sediments, which in this region appear to have released V80% of their P into the water column. Solubilisation of P is likely to involve the release of Prich pore waters from bottom sediments during wind- or cyclone-driven sediment re-suspension events [29]. The timescales for these processes are unknown but are likely to occur over months to many years. The nearshore anoxic zone therefore has the potential to be a long-term source of dissolved P to the marine environment. Although the amount of terrigenous sediment declines with increasing distance o¡shore, the relatively constant Nd concentration at V1/3 of crustal levels in the carbonate-rich reef sediments implies the presence of widely distributed ¢negrained terrestrial components in the reef sediments. This contrasts with the budget for organic carbon derived from carbon isotopic analyses, which show [32] that the terrestrial plant detritus is mainly deposited within V2 km of the river mouth with no terrestrial 13 C signatures being present in the o¡shore reefs. This is consistent with much more rapid recycling of organic carbon compared to the rare earth element Nd, the latter essentially remaining ¢xed in the sedimentary column. Furthermore, since Nd is derived almost exclusively from the land, its isotopic signature is una¡ected by biogeochemical processes. The Nd isotopic results also show that the relative proportion of basaltic-derived soils in the terrigenous sedimentary component increases with proximity to the coral reef. As the ¢negrained basaltic soils contain high P, they are likely to have a disproportionately larger e¡ect on the ecology of GBR than hitherto realised. Whilst direct measurements of recent deposition rates of terrigenous components into this region of the GBR are limited [23], trace element studies EPSL 6623 22-4-03 Cyaan Magenta Geel Zwart M. McCulloch et al. / Earth and Planetary Science Letters 210 (2003) 249^258 of corals have shown an increase in terrestrially derived sediments by U4^8 since European settlement [30]. It is thus likely that more intense land use, particularly on the basaltic soils, has enhanced the P £uxes. This study therefore provides further support for the need for general adoption of minimum-impact soil surface management practices (e.g. minimum tillage, green cane trash blanketing) combined with measures such as the re-establishment of riparian vegetation zones to reduce transport especially of P-rich basaltic soils into coral reefs. Unfortunately, the e¡ects of the past 100 years of inappropriate land-use practices cannot be rapidly reversed, as drainage lines still contain accumulated ¢ne-grained sediments and in the nearshore environment sediment desorption of P will be an ongoing process. Acknowledgements [6] [7] [8] [9] [10] [11] This project was partially supported by an Australian Research Council grant to M.M. on the quanti¢cation of anthropogenic £uxes to the Great Barrier Reef. We appreciate the helpful comments by Elbaz-Poulichet and anonymous reviewers. We thank E. Bard for pointing out an oversight in our cartography of the Australian coastline.[BARD] [12] [13] [14] [15] References [1] C. Birkeland, Life and Death of Coral Reefs, Chapman and Hall, New York, 1997, 536 pp. [2] S. Carpenter, N.F. Caraco, D.L. Correll, R.W. Howarth, A.N. Sharpley, V.H. Smith, Nonpoint pollution of surface waters with phosphorus and nitrogen, Ecol. Appl. 3 (1998) 12. [3] O. Hoegh-Guldberg, The impact of increased concentrations of ammonium and phosphate on coral growth and survivorship under ¢eld conditions, J. Exp. Mar. Biol. Ecol. 50 (1999) 839^866. [4] D. Weaver, N. Austin, M. McCulloch, R. Banens, E. O’Louglin, B. Prove, P. Hairsine, J. Cox, A. Hamblin, Davis, J. Olley, I. 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