CHAPTER 18 Sp Water and Sediment srt and sediment play an important role in the global geological transport sys- tem that connects the continents to the joceans. The water draining the continents contains chemical elements in solution as well as particles in suspension. The suspended particles are part of the sediment load that is moved continuously by #un- hing water, wind, and continental ice sheets from the continents into the ovean basins. These fun- damental geoto cause the erosion of the continents and the deposition of sed~ iment in the oceans but also affect the chemical componition of seawater “The chemical composition of water on the con- tinents is determined largely by the congruent snd incongruent dissolution of rock-forming minerals, by the sorption of ions to the surfaces of suspended particles, and by the uptake of nutriems by plants and animus. The processes that govern the chemi cal composition of water on the continents are the domain of aqueous geochemistry and have been presented in textbooks by Drever (1997), Berner and Berer (1987. 1996}. Langmuir (19971, Appelo fand_ Postma €1993), Stumm (1990), Stumm and Morgan (1996), Faure (1998, and others “The water. as well asthe sediment enteained in it, contains elements that have radiogenic isotopes, shat formed by decay of their long-lived radioactive ‘parent nuclides in the rocks ofthe continental crust ‘Theretore, the isotopic compositions of Sr. Nd, Pb. Hi, and Os in water and sediment vary depending fon the ages and parent—daughter ratios of the jeal_ processes not on 42 bedrock exposed to weathering in the drainage basins of the continents. In eases where the peology of a drainage basin includes rocks of different ages and chemical compositions, the chemieal and isotopic compositions oF the water and sediment are the resull of mixing of wo or more components. in varying proportions, The isotopic composition and concentration of the elements dissolved in the water of streams and lakes can be used 10 obtain information about the geology of drainage basins. about the rates of weathering of different rocks and minerals, aboot anthropogenic contamination of the surface and subsurface environment, and about the input of these elements to the oceans, The amount of available information for some of the elements is limited because their concentrations in water and sediment are low: (e.g.. Hi and Os) and because much work is still in progress. 18.1 STRONTIUM IN STREAMS The concentrations of Sr in streams and. lakes vary widely depending primarily: on the mineral composition oF the hedsoek and on efimatie fac- tors fPalmer and Osmond, 1992). A review of the literature indicates that surtace water on the Pre cambrian Shield of Canada and in the Appalachian ‘Mountains contains less than 100 j.g/L. (ppb) of Sr Jn most cases, whereas water in the midwestern and southwestern states ofthe United States has high Sr concentrations in excess of SOO jigfL. The suriacewater in the midwestern stules is Sr rich because this region is underlain by marine carbonate rocks of Paleozoie age that contain celestite (S'SOx) and strontianite (S1CO,) (Feulner and Hubble, 1960) The elevated Sr concentrations of water in the southwestern states are attributable to the effects of evaporative concentration caused by the semiarid to arid climatic conditions of this region. ‘The isotope composition of Sr in surface water in a drainage basin underlain by a variety of rock lypes depends on 1. the *'S1/**Sr ratios and Sr concentrations of each rock type, 2. the area of the surface exposure of different rock types, 3. the susceptibility to chemical weathering of the minerals these rocks contain, and 4. mixing of water derived from different rock types in the streams draining the basin. In most eases, the isotope composition of Sr in sur- face water is dominated by the rocks that are most susceptible to dissolution, have the highest Sr con. centration, and have the largest surface exposure, In dition, the isotope composition of Sr in streams changes continually downstream as a result of mix- ing with water of tributaries, groundwater, and sur face runof. These considerations give meaning to the statement that the isotope compositions of Sr snd other elements (e.g... Né. Pb, Hf, and Os) in surface water are controlled in complex ways by the geology of the drainage basin ‘The relation between the geology of a drainage busin and the isotope composition of Sx in streams tnd Takes leads to the insight that the ‘'S1/*®Sr ratios of lacustrine carbonate rocks that were deposited in the gcological past can vary strati- Beaphically only as a result of changes in the geol- ‘ogy of the basin. The geological events that can cause the *Sc°Sr ratios of lacustrine earhonates to change include 1. deposition of voleanic ash or extrusion of lava flows within the drainage basin, 2. exposure of granitic basement rocks or other rock types as a result of the erosion of the basin by ice sheets or stecams, Strontiwn in Soreams 413 3. complete removal of a distinctive Sr source by continental glaciation or stream erosion, and 4. deposition of sediment derived from distant sources by continental glaciation or wind Stratigraphic variations in the Tacustrine car bonate socks of the Tertiary Flagstaff Formation in Utah were first observed and interpreted by Neat et al, (1979), Similar studies of Sr/*Sr ratios of the lacustrine carbonates of the Eocene Green River Formation of Wyoming are by Rhodes et al, (2002) and of '$0/!°0 ratios by Morrill and Kock 12002), ‘The stratigraphic variations of the isotopic com position of Sr. Nd. Pb, Hf, and Os in recently deposited lacustrine sediment also record the onset of industrial and agricultural activities, mining, and human habitation in historical time 18a Rivers, Precambrian Shield, Canada ‘The radiogenic *"Sr in Rb-bearing rocks and mie. crals of Precambrian cratons is released into sur- face water as a result of chemical weathering and is ultimately transported into the oceans (Faure etal, 1967). This phenomenon as illustrated in Figure 16.11 by mixing of the water of Lake Superior (°Sr**Sr = 0,720) with water of Lake Huron (°°S1/"Sr = 0.710). The presence of radio genic *'Sr in surface water on the Precambrian Shield of Canada was first demonstrated by Faure et al. (1963), who analyzed the Sr in mollusk shells from lakes and rivers in northem Ontario, The results confirmed that the Sr in the surface water con the Precambrian Shield of Canada has ele- vated "Se*Se ratios with an arithmetic mean of 0.7163 + 0.0019 for 15 samples relative to 0.7080 for the E&A Sr isotope standard In a subsequent stuly of the 39 largest Canadian rivers, Wadleigh et al. (1985) reported YSr*S¢ ratios ranging from 0.70460. ¢Skeena River. British Columbia) to 0.73844 (Grande Riv- ere de In Baleine, Nouveau Quebec) relative to 0.7080 for E&A, The three largest rivers in Canada have comparatively low "’Se/*Sr ratios hut high Sr concentrations St Lawrence 0.70946, 137 git. Mackenzie 0.71102. 175 gil. Fraser 071195, 80 yell.41418, Water and Sediment A comprehensive study of the isotope compositions of Se, S, O, Cand Hof water in the St. Lawrence River and sts tributaries estending upstream from Quebec City to the southera end of Lake Huron was later published by Yang eal. (1996), The combined discharge of the 39 rivers included in the study by Wadleigh et al, (1985) represents 48% of the total amount of water that drains the surface area of Canada, The average St concentration oF this water can he calevlated from the equation Sty = Sn fr tSr ft St fy UBD were Sr. Sts. Sho a the concentrations of Sr in water of rivers 1.2... nD. yp SD. SD, fee he and Dy. Ds.....Dy are the average annual dis- charges of the individual rivers included in the summation. The resulting average Sr concentration weighted by the discharge of each of the 39 rivers, is 3.6 pall. The average “'SrSr ratio of the water weighted by both the Sr concentrations and the Uischarges of each of the 39 rivers is obtained from the equation sent * (se) Se res (S3),sun where Sry = 83.6 ug/l. and the f factors: are derived! from the discharge asin equation 18.1 The weighted-average "'Sr/*Sr ratio of the 39 Canadian rivers included in the study by Wadleigh ct al. (1985) is O.71184, which is & more appro- priate estimate of the isotope composition of Sr in surface water than the unweighted arithmetic mean of 0.71703 calculated from the same data The wide range of 'Se/Sr ratios and Sr concen: trations of the Canadian rivers included in the study of Wadleigh et al. (1985) reflects the diversity of the rocks in their drainage basins, The average con ‘centrations and isotope ratios of Sr in the rivers that ‘Table 18.1. Average Sr Concentrations and ’Sr/*Sr Ratios of Rivers on the Precambrian Shield of Canada in Relation to the Ages of the Rocks Underlying Their Drainage Basins Tectonic Age, Sr Province Ga igi. “sef*Sr Superior” 32.596 0.7295 6-14 0.71855-0.73844 Churchill” ~1.8 156 0.7248 8-23 0.71882-0.73013 Grenville ~1.0 126 0.7151 7-23 0,71307-0.7 1864 Paleozoic! <0.6 875 0.71170 59-137 0,70946-0.71563, Sources Waaleigh etal, 1985. Notaway, Rupert, La Grande, Eastman, Aux Feuales, § la Baleine, Grande Rivere de Ia Baleine. and Amaud "Koksoak, Chuzchill (Mansobs, Back, Thelon. and Karn CChurshill Labrador, Newioundland), Saguenay, Man- cougar, Pett Mevitina, Moisio, Aux Outardes, and Natasha $1, Lawrence, Fraser, Columbia, and St. Sohn Grain the major tectonic provinces of Canada are listed in Table 18.1 The results demonstrate « consistent relation- ship between the " Sif"Sr ratios of rivers and the crustal stabilization age of the tectonic. province iin which these rivers occur. For example, the highest “"'Si*Sr ratios (0.71855-0.73844) exist in rivers draining the Superior tectonic province. Which was subjected to the Kenoran orogeny at about 2.5 Ga (Section 6.7). Low "Sd**Se ratios «0,70946-0.71563) occur in sedimentary rocks of Paleozoic age in the area south anal west of the Hudson Bay, in the St. Lawrence owlands, in southwestern Ontario. and in southein Alberta SUill lower "'$e?"*Se ratios (0.7046-0.70542) were reported from the Skeena, Nass, and Stikine Rivers in British Columbia where voleanic rocks of Ceno- Zoie ages are exposed. In addition, Table 18.1 demonstrates that the rivers draining igneous ard metamorphic rocks have uniformly low Sr concen- trations ranging from 6 to 23 ug/L. whereas the rivers draining sedimentary rocks of Paleozoic ageCanadian Rivers Draining Rocks of Precambrian and Paleozolc Ages Superior 0 2 4 «60 80 100 120 (1181) « 10° ppo-? Hout 161 Mixing of water draining igneous and nietamorphie rocks of the Superior tectonic province and sedimentary rocks of Paleozoic age fn the Precamirian Shield of Canada, The rivers Albany, Severn, Moese, Winisk. Porcupine. Hayes, Atawapiskat, and Hatricana, The rivers draining only the Superior weetonie provinee and. Paleozoic sedimentary rocks are identified in ‘Table 18.1, Data from Wadleigh et al. (1995), have much higher Sr concentrations between $9 and 137 wall. ‘The drainage basins of several Canadin rivers are underlain by the schists and gneisses of the Superior tectonic province as well as by sedimentary rocks (including carbonates) of Paleozoic age. The Sr isotope ratios of the water in these rivers are consistently lower than those of rivers that drain only rocks of the Superior tectonic province. The rivers that drain both types of rocks have an average “'S1/"Sr ratio of 0.7155 + 0.0015 (25, N=9) and an average Sr concentration of 39.9 11.8 gil (27, N-=9), These values define a point close to the Sr isotope mixing fine in Figure 18.1 and thereby confirm that the Sr in these rivers is @ mixture of two components originating from rocks of the Superior Province and from Paleozoic sedimentary rocks. The abundance of Sr derived from the Paleozoic rocks (f) is calculated from equation 16.4 Sty = Stpus P+ Stsy 1 — f) Strontium in Streams — 415 309= 8751496) (18.3) f=040 “This result demonstrates that the Srerich water raining Paleozoic carbonates effectively depresses the Sd"Sr ratios of Sr-poor water draining igneous and metamorphic rocks ef the Supe- rior Province, Another noteworthy result that arises from the ‘work of Wadleigh ef al. (1985) is that the data in Table 18.1 define a straight line in Figure 18.2, The equation of this line is = (28) 420(8) na from which the Rb/Se ratio of the surface rocks of the Canadian Shield can be estimated: (Rb ) “srr ~ O7S1/Sn): ne "sr e740 0.730 0729 710 Sr 0.70% Y 2 3 Geoioge age, Ge oeNt 2 Average *7S¢**Sr ratios of Canadian rivers draining tectonic provinces of different ages: S = Superior, C = Churchill: G = Grenville: P = Paleozoic. The error bars are two standard deviations of the mean, as indicated in Table 18,1, Data from Wadleigh et al, (1985),416 18, Water und Sediment Since the rivers draining rocks of the Superior twetonie province have SrM*Sr = 0.7295 and since (*"Sr*Sr), = 0.7055 (Figure 18.2), (2) _ 0.7295 — 0.7085 Br) ge 2.89 x 142 x 10-25 x 10? = 0.234009 This value is similar to direct determinations of the Rb/Sr ratio of igneous rocks compiled in Figure 18.3 ‘The results of Faure et al, (1963) and Wadleigh ‘etal, (1985) demonstrate that the rocks of the Precambrian Shield of Canada, like other cratons on the continents of the world, are releasing radiogenic "’Sr into the oceans. However, the Sr-rich water Re Sr b/Sr Ratios of L Igneous Rocks rep Grente @ rab ose Monzorite ¢ 0.4 0.23 +0.09 — =, —* Granodiorite 0" Diorte ‘Gaboro TTT eT rt Rock type cURL ms Average RbSr ratios of igneous rocks ranging in composition from gabbro to granite. ‘The RbVSr ratio of the Canadian Precambrian Shield derived in Figure 18.2 from the "SS ratios of river water (0.23 + 0.00) implies that the rocks range in composition from diorite t9 agranodiorite. Data from Faure (1978). draining marine carbonate rocks of Phanerozoie age masks the elevated “'St/Sr ratios of the Sr-poor water draining Precambrian eratons. ‘The chemical compositions and the isotope ratios of Sr and other elements in the major rivers of the world have been studied in order to derive information about the rates of chemical weathering under various climatic conditions and to quantify the fluxes of dissotved elements and suspended sediment being transported from the continents to the oceans: Weathering: Gaillardet ct al., 1999, Chem Geol, 159:3-30. Benedetti et al, 1994, Chem. Geol., 118:203-220, Viers et al, 2000, Chem. Geol, 169:211-241, Probst et al.. 2000, Chem. Geol., 170:203-219. Baltic Shield: Wickman and Aberg, 1987, Novdic Hydrol., 18:21~32. Aberg and Wick- rman, 1987, Nordic Hydrol, 18:33-42, Lifven- dahl etal, 1990, Aguar. Sci, 52:31S-329. France: Semhi ct al 168:173-193, 2000, Chem. Geol, Himalayas: Pande et al. 1994, Chem. Geol 116:245~259. English et al. 2000, Geochim. Cosmochim, Acta, 64:2549~2566, Demy and France-Lanord, 1996, Earth Planet. Sci, Lett. 142:59-74 South America: Palmer and Edmond, 1992, Geochim. Cosmochim. Acta., 56:2099-2111 18.1b Groundwater, Precambrian Shield, Canada ‘The chemical-weathering reactions on the Pre- cambrian Shield of Canada may achieve a state of equilibrium when the "’Sr!"°Sr ratios of the water approach those of the rocks. For this rea- son, MeNutt et al, (1987) measured the "’Sr!*Sr ratios of a large number of whole-rock samples of the Bast Bull Lake intrusive in the Superior Province of Ontario and compared them to the "S/S ratios of groundwater collected from deep diamond-drill holes in the same intrusive‘The East Boll Lake pluton is located northwest of the town of Massey, Ontario, on the north shore of Lake Huron, close 10 the southem margin of the Superior Province. It is composed of layered mafic rocks ranging in composition from anorthosite t© granophyre and yielded a U-Pb concordia date of 2480 10 Ma based on analyses of zircon and baddeleyite (Krogh et al.. 1984). The whole- rock samples of the Kast Bull Lake intrusive analyzed by MeNutt et al. (1987) seatter widely on the Rb-Sr isochron diagram in Figure 18.4 and do not satisty the assumptions for dating by this method. A selected set of unaltered samples yields a Rb-Sr errorchron date of 1.8 Ga, whereas the altered samples taken from four fracture zones in deep cores lead to a Rh-Sr date of 0.65 Ga. Neither one of these dates can be attributed to a recognisable geological event. Strontium in Streams ANT 28 samples relative to 0.7080 for E&A. The isotope ‘composition of Sr in secondary minerals (laumon: tite. calcite, and gypsum) recovered from fractures in the cores is similar to that of the groundwa- ter_with an_average *'Si?*Sr ratio of 0.71289 (0.71102-0.71963) for 14 samples. The whole-rock samples of the East Bull Lake complex have a wide range of *7S1/**Sr ratios between 0.70478 and 0.7151 with a mean of 0.70943 for $7 samples, The "'Srf'Sr ratios of the bedrock of the East Bull Lake complex overlap those of the groundwater and the fracture minerals. Therefore, the Sr im the groundwater could have originated from the bedrock by selective dissolution of rocks and/or minerals whose *7Sr!™°Sr ratios were in the East Bull Lake Intrusive, “The ‘water samples have average concentra 20+ Ontario Ganeda tions of Sr = 61.7 (5-148) jg/L and Rb = 26.7 3 (20-40) igi. with an average RbySr ratio of 0.43, 2 | Groundwater ‘Two water samples with anomalously high Sr con- 2 vol centrations (2310 and 2900 g/L) were excluded from the average. The histograms in Figure 18.5 r indicate that the groundwater has an average oO 14 “Se Sr ratio of 0.71306 (0.71074-0.72023) for 0704 0.708 O712 A716 Secondary 10} minerals Sst East Bull Loke Intrusive, Ontario 2 =I a eb ore 24 c o700 0708 0712 0716 20k Bedrock 3 aL nates a ee ore . ° 4 rr 0704 0708 o712 0716 Herke iss Errorchrons of unaltered and altered whole-rock samples recovered in drill cores from the East Bull Lake intrusive located in Ontaris near the southern edge of the Superior structural province. The U-Pb concordia date of the intrusive is 2480 + 10 Ma (Krogh ct al.. 1984), Data from MeNutt et al. (1987). ‘SPS: cae 5 Histograms of ©'St/*Sr ratios of ‘groundwater, fracture-filing minerals, and bedrock samples of the East Bull Lake intrusion, Superior tectonie province, Ontario. Canada, The *’Sr/**Sr ratio of E&A was 0.7080, Dats from McNutt etal. (1987),41818. Warer and Sediment upper part of the range of this ratio in the bedrock The required selectivity of this process implies that the groundwater was not in equilibrium with all of the rock types represented in this complex. On the other and. the good agreemem between the isotope composition af Sr in the groundwater and (he fracture minerals means that these minerals could have precipitated in the relatively zeeent past from the groundwater that oceury in the East Bull Lake intrusive at the present time. The discrepancy between the “Se/*Sr ratios of the groundwater and the becrock of the East Bul Lake complex may also be the result of mixing of two components of water that originated from the Archean gneisses of the Superior Provinee an from the East Bull Lake complex. If these hypothetical components are characterized by having different “'Sc/"Se ratios and different Sr concentrations. the groundwater samples in the East Bull Lake complex should detine a straight line in coordinates of the “'Se"Sr and W/Sr ratios, ‘The data points in Figure 18.6 actually detine several straight lines instead of a single line. Therefore, the ground ater consists ef several two-component mixtures that do not appear fo be in communication with each other The Stich waters have low “'S**Sr ratios between about 0.710 and 0.712, whereas the low Sr waters have high “"Se™'Sr ratios ranging up to 0.720 (not shown in Figure 18.6). The Srerich waters probably originated by weathering oF the plagioclase-bearing rocks of the East Bull Lake intrusive, The low-Se water with high ~S1/°Sr ratios may have originated from the Archean ‘granitic gneisses into which the East Bull Lake complex was intruded. These groundwaters ater acted primarily with mieroctine, muscovite, and biotite, which have lower Sr concentrations. than plagioclase, are more resistant to chemical weather- ing than plagioclase. and are enriched in radiogeni ‘Sr because of in situ decay ot Rb. ‘The isotopic compositions of Sr and chemical compositions of groundwater. mineral water, and oilfield brines elsewhere m the world have been used to study a wide range of phenomena: Chemical and Isotopic Evolution: Bullen et al.. 1996. Geavhim. Cosmochim. Acta, 60: 1807-1821, Bullen etal. 1997. Geochim, Cosmochim, Acta, 61:291 306, Négrel et al. Sr Se | Groundwater, East F Bull Lake intrusive, Ontario o.7e0 one b / 0.716 Le ora ore n ° ° 20 40 60 (1/Sr) x 10° ppb * vas em Strontium: isotope mixing nes defined by groundwater in the East Bull Lal Superior tectonie province, Ontario, Canada, ‘Three samples plot off-seale, Data from MeNutt etal. (1987). fc intrusive, 2001, Chem, Geo. 177-287-308. Naftz et al. 1997, Chem, Geol, 141:198—208. Subsurface Brines: Sass and Starinshy 1979. Geochim. Cosmochim, Acta, 43:885— 895. Starinsky et al. $9834, Chem. Ge. (Iootupe Geosci. Sect}, 1:257-267. Starinsky vial, I983h, Geochim, Casmuchim, Acta 4:687 -695, Chaudhuri et al., 1987, Geochim. Cosmochim. Acta, SUAS-53, Lowry et al 1988, Appl Geochem.. 2177-184. Stacber and Walter. 1991, Gevehim, Cosmochim, Acta. 55:309-325. Geothermal Waters: Négrel_ et al. 1997, Chem. Geol. 135:89-101, Négrel et al, 2000. Appl. Geochem.. 15:1345—1367. Grimes et al. 2000. Chem. Geol.. 163-247-265,Repwnitories of Nuclear Waste: Peterman and Wallin. 1999, Appl. Geochem., 14:939— 951 Stuckless et al., 1991, Scrence, 254:551— 354, Saline Groundwater in Precambrian Cra- tons: Gascoyne etal. 1987, in Frit and Frape (Eds). Geol. Asso. Can. Spec, Paper. 35:53-68, Frity and Prape, 1987, Geol. Assoc Canada, Spee. Paper. 33:210pp. McNutt etal, 1990, Geochim. Cosmochim, Acta, 54:205-215, Nurmi et al, 1998, Appl. Geo- ‘hem... 2 185~203 Fracture Minerals: Bottorizy. 1987. Appl Geochem., 2:81-92, Bottomley and Veizer, 1992, Geochim. Cosmochim. Acta, 56:369— 388, Larsson and Tullborg, 1984, Lithos. 17:117-125, Wallin and Peterman, 1999, Appl. Geochem., 14:953-962, Speleothems: Verheyden et al., 2000. Chem. Geol. 169:131—144, Goede et al.. 1998, Cher, Geol. 149:37-80, Additional references on the regional flow of groundwater in North America are listed in Sections 55a. 5.5b, 10,12a, and 10.12b, 18.2. SEDIMENT IN STREAMS ‘The sediment being transported by streams includes _gcains of resistant minerals (e.g.. quartz, K-feldspar. muscovite. zircon, gamet) as well as weathering products (e.g. exyhydroxides of Fe, Al, and Mn, Kaolinite) and particles of organic matter. In addition, cations of chemical elements in solution are sorbed by films or organic molecules that cover the surfaces of the sediment particles. The organic matter that coats the mineral grains has negatively charged surface sites at_near-neutral pH and therefore sorbs Sr°~ and cations of other elements from solution, “The isotopic compositions of certain elements (e.g, Sr, Nd, and Pb) that are sorbed to colloidal particles (diameters less than 1 um) are similar 10 the isotopic compositions of the elements in solution, Particles of resistant minerals with Sediment in Streams 419 diameters larger than about 1 yum in_diameter contain Sr, Nd, and Pb, whose isotope compositions difer from those of the sorbed fraction hecause they ‘depend on the ages of the mineral grains and on the respective parent-daughter ratios, ‘The elements in solution originated by the congruent or incongruent dissolution of minerals that are susceptible 10 weathering (e.g. calvite, sulfide minerals, plagioclase) that generally have low parent—daughter ratios (Blum et al. 1993) ‘Therefore, the elements that are sorbed trom solution t0 the surfaces of colloidal mineral grains are less enriched in radiogenic isotopes. than the same elements contained within the coarser resistant grains. Although sediment particles. of all sizes sorb ions from solution, the sorbed fraction is dominant among the colloidal particles because, collectively. they have lager surface areas than the coarse sediment grains with diameters >1.0 um. ‘The sorbed fractions of Sr. Nd, and Ph in sediment can be recovered separately by leaching sediment samples with dilute acid, which causes the sorbed fraction 10 be released into solution without affecting the fraction of the elements that is contained within the resistant mineral grains ‘The isotopic compositions of sorbed Sr. Nd. and Ph provide information about the minerals that are weathering in the drainage basin and bout anthropogenic contaminants that are released info streams in the form of fertilizer, municipal cllluent, and industrial wastewater. The isotopic ccompesitions of Sr, Nd, and Pb in cesistant mineral rains can be used fo identify their provenance by dating samples of the bulk sediment or individual minerals grains. In cases where the resistant mineral rains are derived from two oF more sources having different ages or chemical compositions or both. samples ofthe bulk sediment can be treated as wo. or three-component mixtures. An example of 1wo- ‘component mixtures of sediment from the Real Sea was presented in Section 16.6b. 18.24 Murray River, N.S.W., Australia The relation between the diameters of sediment grains and the concentration and isotope ratios of Sr was demonstrated by Douglas et al, (1995) in42018. Water and Sediment 4 study of the Murray-Darling river system in New South Wales, Australia, The drainage basin of these rivers has an area of more than 1.0 x 10" kn and is underlain partly by granitic plutens thar intruded detrital sedimentary and metamonphie rocks of eatly Paleoroie age. Theye rocks form the Great Dividing Range, which extends parallel tw the southeastern coast of Australia between Melbourne in the south and Brisbane an the north, In addition, deposits of Cenozoie sand. silt, and clay are exposed in the central and western part oF the hasin, The climate of the Murray Darling drainage system is subtropical in the north. temperate in the son. semiarid in the west, and alpine inthe Great Dividing Range in the east. The chemical compositions of the coarse par- ticulate sediment fraxsion ia Table 18.2 ean be used (0 caleulate its mineral composition (norm) by standard methods presented by Faure (1998, Section 19.2). The results indicate that the >25- jim fraction contains 53% quamz, 19.5% kaolinite, 11.3% K-teldspar, 80% plagioclase, 4.8% mag- netite. and 2.85% miscellaneous other constituents Table 18.2, Chemical Analyses of Selected Size Fractions of Sediment in the Murray River at Merbein, N.S.W., Australia, Recalculated to 100% Concentration, Sediment 25 yom 1-02 jem 0.006-0.0098 urn Sir WS Sas 286 To. Oss os 006 AI:0s nya 3H F041) 499 1300 Ba MnO 0090.09 008 M0 Lis 230 153 30 027 09 167 Na0 oT 096 293 KO) 193199 223 Quarts S80 6 Kaolinite ws 471 Keteldspar 11.38 Plagioe so Its Magnatite a8 1B Miscellancous 28 39 Sources Douglas ea). 9S Gexthte ‘The normative mineral compositions of the >25- and 0.2-1.041m sediment fractions in Table 18.2 are compatible with the geology of the drainage basin of the Murray River. However. the graph- ical representation of the chemical compositions in Figure 18,7 demonstrates that the concentrations of Nas. Cx, MgO. and KzO rise with decrease ing grain size in the colloidal sediment fraction. whereas the concentrations of SiO>, Fez0:, and AlzOs decrease. Consequently. the chemical com- positions of these fractions do not provide enough Al;Os and SiO: to accommodate the rising com centrations of Na:O, CaO, MgO. and K:0 in aluminosilicate minerals. Evidently, the chemieal compositions of these colloidal sediment fractions are controlled by the sorption of ions rather than by the minerals of which the particles are composed. 100 $$ t Murray River at Merbein, Austral wo Concentration, log igeain size), um ovke is Variation of the concentsations of major-element oxides in size fractions of sediment in the Murray River at Merbein, N.S.W Australia, after exeluding organic matter by recalculating the analyses to 100%. Data from Dougias et al, (1995),Murray River Merbein, Australia 8 Bo 8 st 8 aR g Concentration Rb and Sr, ppm ° [Solution | Colloids | Particulates: 4 2 9 2 logtgrain size), rm Havel ks Variation of the concentrations of Rb and Sr with the diameters of the sediment grains in the Murray River at Merbein, Australia: particles in suspension, >25 to L jum: colloidal, ‘<1 to 0,003 jim: solution, <0.003 jm, Data from Douglas e¢ al, (1995), ‘The concentrations of Sr in five different size fractions of sediments in the Murray River at Merbein in Figure 88 increase with decreasing ‘grain size, whereas the Rb concentrations rise to maximum in particley with diameters between 25 and I jam and then decline in smaller particles The "’Sx"Sr ratios of the various size fractions decrease from 0.73540 (1.025 jum) to 0.71601 in the colloidal fraction (0.003—0.006 jum) ‘The data in Figures 18.7 and 18.8 reveal sys- tematic differences in the enrichment of alkali met- als by Sorption in the colloidal fractions relative to the particulute fractions: Na > K > Rb. In addi tion, the alkaline earths are enriched by somption such that Ca > Mg > Sr. The cause for the pref ‘erential sorption of Na! and Ca°* relative to their respective congeners is not apparent from the avail- able data The *Sr!*Sr ratios of the colloidal particles (0.003 -1.0 jm) and the reciprocals of their Sr con- 25 jum; 2. 10-25 pm; 3.0.2-1.0 jum; 4, 0.006-0.2 jum: 5. 0.003-0.006 jm. The open triangle represents the Sr in solution in the water. Data from Douglas etal. (1995). smallest colloidal particles (0.003-0.006 jim) are Similar to thove of the dissolved Sr (<0.003 jim). ‘The interpretation of these data proposed by Douglas et al. (1995) is that the colloidal par- ticles contain two isotopic varieties of Se. One of these is sorbed from solution to organic films that ‘coat the grains while the other s the Sr that resides within the grains and whose 'Sr!*Sr ratios were increased by decay of *"Rb prior to weathering. ‘The fraction of sombed Sr in the colloidal parti cles increases with decreasing grain size because the amount of organie matter coating the grains and their surface area both increase. ‘The large suspended mineral particles with diameters greater than 1 jim deviate from the mixing Tine of the colloidal panicles in Figure 18.9 because most of the Sr they contain resides within these mineral grains and only a small fraction of it is sorbed. As a result, these grains are be isotopically heterogeneous because the ratio of each grain depends on ity RbvSt ratio and2218, Water and Sediment Murray River Merbein, Australia 200 o 2 4 60 Loss on ignition, % Hecke isa Relation between organic matter measured by loss on ignition and the Sr concentrations of colloidal and particulate sediment in the Murray River at Merbein, Australia, The size fractions are identified by number: 1, =25 om: 2. 1,0-25 wm: 3. 02-10 yum: 4, 0.006-0.2 yam: 5, 0,003-0.006 jum. The Sr concentration at LOT = 0 is about 50 ppm, Data from Douglas et al, (1995), fon the geological age of the mineral of which it is composed. The importance of the fitm of organic mat ter fo somption of St°* and other ions on mineral ‘grains im the Murray iver at Merbein is indicated in Figure 18.10 by the relation between loss on ignition (LON) and the Srconcentration of colloidal and particulate sediment. The data demonstrate that the high Sr concentration (326.9 ppm) of the small est grain size (0.003-0.006 pm) 1s attributable to the fact that the organic film coating these grains makes up nearly 70% of their wveight. The com- paratively low Sr concentration (59.1 ppm) of the largest grains (>25 jum) is related to the fact that the organic film coating these grains. constitutes, only 12.4% of their weight even though the coating has about the same thickness as that which covers, the smaller colloidal particles, An extrapolation to LOI = 0% in Figure 18.10 indicates that the min- crals of the particulate sediment have an average Sr concentration of about 50 ppm. the colloidal sediment sorbs Sr°~ ‘Therefore. the RbiSr ratios of the colloidal sediment decreases trom 1.52 in the 0.2-1.04\m traction to 0.0458 in the 0.003-0,006-;sm_ traction, In addition, the “"Se/"Sr ratios of the colloidal sediment decrease trom 0.72208 (0.2-1.0 jum} 10 0.71601 (0.003-0.006 jum) and correlate positively with the “'RD/Sr ratios in Figure 18.11. The straight line defined hy the three colloidal fractions, has a slope m = 0001417 that yields a Rb-Sr date of 100 + 2 Ma (Douglas et al, 1995). This date is fictitious because the colloidal sediment fractions define a mixing fine rather than an isochron $8: —“waray aver Merbeln, Australia 0.735 x 0.730 / 0.725 a a720+ a8 4 omsP ‘CHUR.Sr "Rb Sr rover isa Mixing line defined by the colloidal fractions of sediment (solid circles) in the Murray River at Merbein, Australia, in coondinates of the "'Sui*Sr and “RbISr ratios The fictitious date derived trom the slope of the mixing fine is 100 2 Ma, The particulate traetions crosses) of the sediment are composed primarily of minerals whose approximate Rb-Sr model date relative 0 CHUR is 370 Ma (Late Devonian to Early Pennsylvanian), The size fractions are identified by mumber: 1, =25 wm: 2. 1.0-25 um: 3 0.2-1.0 pm: 4, 0.006=0.2 1m: 5, 0.003-0.006, ‘The open triangle is the soluble Rb and Sr. Data from Douglas et al, (1995),‘The coarse fractions of the sediment are composed of mineral grains whose *'Sr/°Sr and “'RbMSr ratios are not significantly affected by sorption. Therefore, they retain a record of the dates of their crystallization, For example, the Rb-Sr systematics of the =25..m traction (1 in Figure 18.11) can be used to calculate a Rb-Sr date relative to CHUR-Sr baxed on the equation (=e CF )ia 2 = (Sy =) (=) ass) ~ (55), Csr si ° Given that ge)" nse? aor (TS) =o7st6 (Sean Te) (2), = os (BE) -sm Then 07045 — 0.0816\e*" — 1) = 0.73163 — 5.2221 — 1) and PS [a2 lO This date is only an approximation of the age of the mineral grains because the sediment may be a mixture of grains having different crystallization ages, because RWSF ratios of some of the grains may have been altered by weathering, and because their initisl *’SePSt ratios may differ. Nevertheless, Rh-Sr dates of individual unal- tered mineral grains or of collections of grains that originated froma single source provide information concerning the provenance of the sediment. The geological value of this information is enhanced ‘when the sediment being dated was deposited in the geological past (eg. Mulfier and Doe, 1968) ‘The relation between river sediment in the Namoi River, a tributary of the Darling River, and soils of its drainage basin was investigated Sediment in Streams 423 by Martin and McCulloch (1999) using chemical analyses and isotope ratios of Sr and Nd. 18.26 Fraser River, British Columbia, Canada ‘The Fraser River of British Columbia drainy an ‘area of 2.38 x 10° kin? that includes a wide variety ‘of rocks along the active westem margin of the North American continent (Cameron and Hattori 1997). The water and sediment it discharges into the Pacific Ocean originate from four tectonic units identified in Figure 18.12, starting with the Foreland belt at the source of the Fraser River. followed by the Omineca belt, the Intermontane belt, and the Coastal belt from east to west. The rocks of the Foreland and Omineca belts consist of Late Proterozoic and Paleozoic sandstones, shales, and carbonates, but the Omineea belt also contains matic igneous rocks derived from the mantle, The Intermontane belt is composed of several accreted terranes and consists of interbedded sedimentary Fraser River, British Columbia iouae 18,2 Drainage basin of the Fraser River, British Columbia, Canada: F = Foreland belt; O = Omineca belt: I = Intermontane belt, C= Coastal belt; PG = Prince George: and Q= Quesnel, Adapted from Cameron and Hatori (1997)42418. Water and Sediment and voleanie rocks (Late Triassie to Early Tertiary) iniruded by granitic plutons. The Coastal belt is underlain by metamorphic rocks of Permian to Cretaccous age intruded by quartz~diorite plutons and overlain. by Andean-type voleanic rocks of Cretaceous to Tertiary age “The Fraser River in Figure 18.12 arises near ‘Mt. Edith Cavel in Jasper National Park and flows northwest within the Rocky Mountain Trench, which is the boundary between the Foreland belt and the Omineca bell, to the town of Prince George. where it turns southwest and erosses the Intermontane belt to the Coastal belt. It tums west at the town of Hope and enters the Pacific Ocean at ‘Vancouver, There are no dams on the Fraser River. Which means that the sediment discharged into the Pacitie Ocean represents all of the rocks exposed to weathering in its drainage basin. Cameron andl Hatton’ (1997) collected water samples from the Praser River and its tributaries and recovered the suspended sediment by’ passing the water through 0.45-j.m filters. Therefore, theit sediment data pertarn primarily to the silt and clay sige fractions, Wadleigh et al. (1985) previously reported an” Si!*Sr ratio of 0.71195 relative to 0.7080 for E&A and a Sr concentration of 80 jeg/l in one sample of filtered water th 45 rm) collected near the mouth of the Fraser River ‘Cameron and Hattori (1997) demonstrated that the “Sre*Sr ratios of water and sediment ditter at all of the sites along the course of the Fraser River, although the isotope ratios of oth water and sediment in Figure 18.13 decline with distance from the source of the river, In the upper reaches, of the Fraser River. the “'Srf*°Sr ratios of the sediment samples are higher than those of the water because of the resistance to weathering of Rb: rich mineral grains derived from source rocks of Proterozoic 1 Paleozoic age. In the vicinity of Quesnel, about 550 km downstteam of the source of the Fraser River, the * a sediment drop helow the "'SdMSr ratioy of the water because oF the introduction of sediment derived from malic igneous Tocks by tributaries that drain the Inermontane and Coastal belts (e.8. Nechako, Blackwater. Chileotin, and Bridge), all of which emter the Fraser River from the west The *”Sn!Sr ratios of the eastern tributaries (e McGregor, Quesnel. and Thompson) are similar 10 e 8: | Graer River, Bish Colombia 0.760 Foreland | Intermontane | Coast 0.740}- 0.720 070 ° big F gr | 0.760 | L Sediment 0.740 0.720 | ; 0.700 ‘0800 400 6008001000 Distance rom source, km ricer isis Longitudinal profiles of the “'S1"°Sr ratios of water and suspended sediment (0.45 jum) of the Fraser River, British Columbia: PG = Prince George, Q = Quesnel. ‘The tributaries (open circles) are identified by umber: 1 = McGregor (Foreland); 2 = Nechako Clntermontane); 3 = Blackwater (Intermontane) 4 = Quesnel (Intermontane and Omineca): 5 = Chileotin (Inermomtane): 6 = Bridge (coastal); 7 = Thompson (Intermontane and Omineca), Data from Cameron and Hattori (2997). those of sediment in the Frayer River at the sites where these rivers enter their master stream, ‘The isotope ratios and concentrations of St in water of the Fraser River near its mouth at Alexandra Bridge, a few kilometers upstream of the town of Hope, are the result of mixing of the waters of its tributaries. The “"Sd"*Sr ratio and Sr concentration of the Fraser River at this site (0.7127, 85 jugie) define a point in Figure 18,14 that lies on the mixing line defined by its eastemand western tributaries: Eastem SSF = 0.7149, Sr = 85.6 pel tributaries SF Western a tributaries St where the average *S1/Sr ratios were weighted by the Sr concentrations of the water in each group of tributaries. Use of the lever rule indicates that approximately 80% of the water in the Praser River at Alexandra Bridge near Hope originated from the eastern tributaries (i.e., the MeGregor, Quesnel, and “Thompson rivers) ‘The sediment in the Fraser River at Alexandra Bridge in Figure 18.14 ("'S1**Sr = 0.7098, Sr = 249 ppm) is also a mixture of sediment contributed by the eastern and western trib Eastem 7128, Se= 239 ppm Wester 07087, Se= 2796 ppm a ‘ue: bencoun i Easter tibutaries. soa went soi i otf een aes (81) «10%, ppb (St) « 10%, ppb ™ HORE i612 Two-component isotopic mixing diagrams of Sr in water and sediment of the eastern and westem tributaries of the Fraser River. British Columbia. The points representing water aand sediment of the Fraser River near its mouth lie on the respective mixing lines and indicate that 784 of the water and 67% of the sediment originated from the eastern tributaries. Data from Cameron and Hattori (1997). Sediment in Streams 425 ‘The point representing the suspended sediment in the Fraser River at Alexandra Bridge, like the Sr in the water, i located on the mixing line in Figure 18.14 defined by the sediment of its tributaries. ‘The estimated abundance of sediment contributed by the eastern rivers (70%) is Tess than that of the water derived from these rivers, either because the eastern rivers transport less sediment than the westem rivers or because some of the sediment of the eastem rivers was deposited, The isotope ratios of Sr and Nd of sediment in the Fraser River in Figure 18.15 define an isotopic mixing hyperbola that extends from quadrant I (nvantle-derived rocks) to quadrant 1V_ (crustal rocks), The sediment contributed by the western tributaries (Nechako. Blackwater, Chileotin, and Bridge River) has high ''Nd!'"'Na but low ng ost ‘Ssiant Fraser River, ish Coen 238 Sessa “ Nos Santer ica isis Isotope ratios of Se and Nd of sediment (0-45 jim) transported by the Fraser River, British Columbia, Canada, The tributary rivers (open circles) are identified by nember. Eastern tributaries: 1 = McGregor: 4 = Quesnel: ‘Thompson. Western tributaries: 2 = Nechako: Blackwater; 5 = Chilcotin: 6 = Bridge, E&A Sr standard. “'S1/*°Sx = 0.708048 + 0.000017, NBS 987; *?Sr/Sr = 0.710270 + 0.000019. Tae Nd isotope analyses were corrected for isotope fractionation to “*Nai'Nd = 0.7219 and yielded }Nas#Nd = 0.511868 + 0.000017 for the LaJolla Nd standard, Data from Cameron and Hattori (1997) este ostee ste42618, Water and Sediment °°Se ratios, which characterizes mafic igneous rocks derived from sources in the subcontinental lithospheric mantle, The sediment near the source of the Fraser River (Fitzwilliam) has the opposite isotopic characteristics indicating a source in the Precambrian rocks of the Foreland belt ‘The crustal residence age of the Precambrian basement rocks at the head of the Fraser River can be estimated by reference to CHUR-Nd based on the equation "nay" (3 ")! — -( te) (Gx) - (RS) ier as Substituting the appropriate values for the iso. ope ratios, 0.912638 — 0.1967(6"" — 1) = 05114 = 0.11 — 1) where (Na Na, = OS11435 and C'S "8NGNy = 0.115 (Cameron and Hattori, 1997) Solving Torr. In 1.014372 28» Loy 65x A second estimate of the crustal residence age of the basement rocks at the head of the Fraser River is oblainable from the “Sr*Sr and “Rb Sr ratios of the Sediment (0.7724 and 4.19, respectively): 0.7045 ~ 6 O816(e" 1) = 0.7724 ~ 4.190" = In L.016527 1x08 = 1.15 x 10" y The difference beeen the Sm-Nd and Rb-Sr model dates is attributable to the eflects of weath- ering on the Rb-Sr systematics of the sediment The preferential dissolution of Sr-rich minerals (e.g. plagioclase and calcite) causes the Rb/Sr and “Ser ratios of the sediment 10 rise, The loss of plagioclase does not affect the Sm/Nd ratio ‘of the remaining sediment because the average Sm/NU ratio of plagivelase (0.292) is similar to the average SmvN¢ ratio (0.285) of other silicate minerals. including olivine 10.19} clinopyroxene (0.37), amphibole (0.37), biotite (0.22). K-feldspar (0.14), gamet (0.54), apatite (0.31), and monavite (0.17) (Faure, 1986). Therefore. the model Sm-Nd. date of 2.18 Ga is to be preferred as an estimate of the age of the basement rocks at the head of the Fraser River, 18.3. ZAIRE AND AMAZON RIVERS, The work of Douglas et al. (1995) on the Mur ray River and by Cameron and Hattori (1997) ton the Fraser River suggests that the water and suspended sediment in rivers may be used to Uerive information about several important goo- chemical processes affecting the continents and the oceans: 1. the effect of chemical weuthering of rock: forming minerals on the isotope compositions of Sr, Nd, and Pb in solution in rivers: 2. the average chemical and isotope composition Of these elements in the rocks of the drainage basin and hence in the continental crust: and 3. the rate of erosion of the drainage basin and its dependence on cavironmental conditions, 1cluding clevation above sea level, climate, and Tithologic composition, “These kinds of problenis have been addressed elsewhere: Goldstein et al.. 1984, Earth Planer Sei Lert.. 10:221-236. Goldstein and Jacobsen, 1987, Chem. Geol, Isoiape Geosci. Sect 66:245-272, Goldstein and Jacobsen, 1988, Earth Planet Sci. Lett, 87:249-265. Aberg tal. 1989, J. Hydrol. 109:65-78. Krish- naswami et al. 1992. Karth Planet. Sei Lott.. 109:243-253. Asmerom and Jacobsen, 1993, Earth Planes. Sci, Lett, 115:245~256. Blum et al., 1993, Geachim. Cosmochim. Acta, S7:5019-S025, Négrel et al.. 1993, EarthPlanet, Sci, Lett. 120:59+76. Andersson et al, 1994, Earth Planet, Sci. Lett, 124:195~210. Dupré et al. 1996, Geochim. Cosmochim. Acro, 60:1301—1521, Gaillardet et al, 1995, Geochim. Cosmochim. Acta, $9:3469—3485 Allégee ct al. 1996, Chem, Geol, 131:93-112 Borg and Banner. 1996, Geochim, Cosmochin. Acta, 60:4193-4206, Négrel and Deschamps, 1996, Aquatic Geochim...2:1~27. Henry et al, 1997, Earth Planet. Sei. Let. 146:627~684. Négrel and Groshois, 1999, Chem, Geol. 156:231-249, Négrel et al, 2000, Chem. Geol. 166-271 ~ 18.3a Strontium and Neodymium in Water and Sediment ‘The "'Sr/**Sr ratios of the water in the Zaire and Amazon basins are consistently tower in all eases than the *’St/“Sr ratios of the sediment suspended in the water (Allegre et al., 1996). The difference between the ““Sr/**Sr ratios of the sediment and water is expressed by the parameter (sr “Sr )=[Gs1),,- G5) ]: sn The AC’Sr/*Sr> values of the Zaire and Ama- Te Rhea rep tio he ten owt canes a eae ing values of the “Sr Sr ratios of the sed- iment. In addition, the A(*’Sr/'Sr) values of ai sce han te aa ee ee ee 0.710 a AC"SWSH = 0. Three samples from thks hea Set Mai and asesn a Seman; Sots ioe hs eins ae “he tpi ula Sen he Za 1 ee ho hacen eee mee ee Mace seen Ae ee nd be aes cee eutcaau ing mca case nenisiemioe Remon morta comparatively low Y'SriSr ratios but dissolve preferentially during chemical weathering «Blum Par yOUE) The Resch nile atcha Zaire and Amazon Rivers 427 40 ‘Sr lsotope Disequilibrium aP’seSr 100 aria 0780 0750 0740 G750 *"sc#*S¢ of sediment Isotopic disequilibrium of Se in the suspended sediment and in solution in the water of the Zaire and Amazon Rivers as expressed by AU*SHfS1) = [O'S Stes — C°StP”Sthou] x 100. The *'S1/"Sr ratios are relative to 0.710254 + 0.000006 for NBS.987, Data irom Allegre et al, (1996), in the suspended sediment. resist weathering and have elevated *'S1/*Sr ratios depending on their exystallization ages. ‘The isotope ratios of Sr and Né of the sus- pended sediment in the Zaire and Amazon river systems define tw overlapping data fields in quad- rant IV of Figure 18.17, The scatter of data points reflects the heterogeneity of the parent~daughter ratios and of the orustal residence ages of the rocks in the respective drainage basins. The suspended sediment in sivers is an imper- fect sample of the bedrock exposed to weathering in their drainage basin, not only because of the preferential dissolution of certain minerals fe... pla- Figclase, calcite) but also because the topography of the basin affects the delivery of sediment to the streams and because of the preferential deposition and entrainment of sediment by streams based on the density. volume, and shape of the mineral grains. AS a result. the average isotope ratios of bulk sediment (>0.2 jm) in the drainage of the Zaice and Amazon Rivers in Table 18.3 are prob- ably skewed in favor of minerals that resist weathering and that have physical properties that428 18, Water and Sediment Sua Suspense Saaiment Amazon assae a Cd Payor Hoke Ist Isotope ratios of Sr and Nd in sedimtent suspended in the Zaire and Amazon Rivers and their respective tributaries. The data points are located in quadrant IV defined by CHUR. The stars are the average isotope ratios of each river system, Data from Allegre ef al, (1996), Table 18.3, Average Concentrations of Sr and Rb and Isotope Ratios of Sr and Nd of Sediment in the Zaire and Amazon Rivers and Their Tributaries Parameter Zaire Amazon Rb, ppm 589 002 Sr. ppm 61.0 40-78) 96.7 (40-176) “Rb/ Sr 279 179 “suf sre 0.73155 0.72341 'Smv#Nd 0.1087 0.1025 'SNas4Na 0811803 0.511996 Source: Allegre etal, 1996. ‘Weighted by Sr voncentrations. NBS 987; “Se("*Sr 0.710254 = 0.000006; Lalolia Nd sandscd: "NW "Na = 0.511850 + 0.000010, facilitate their transport in streams, Nevertheless. the data in Table 18.3 do characterize the isotopic compositions of Sr and Nd of the rocks in the Tage drainage basins of the Zaire and Amazon basins. In addition, these data constrain the isotope composition of crustal St and Nd that may enter mantle-derived magmas that intrucle the continen- tal crust, 18.3b Confluence at Manaus. Brazil ‘The city of Manausis located atthe confluence of the Solimbes and Negro Rivers, which together form the Amazon River in Figure 18.18. (The Solimoes River may also be considered to be an upstream extension of the Amazon River). Therefore, the chemical and isotope composition of water in the Amazon River downstream of Manaus is controlled by mixing of these rivers provided that the elements under consideration are conservative, The concentrations of St, U, and Pb in Figure 18.19 indicate that the U concentration of water in the Amazon River (0.033 ppb) downstream of the confluence is only about 7% less than predicted by the mixing model. ‘whereas the concentration of Pb (0.07 ppb» is more than 50% Jower than its predicted concentration (0.15 ppb). The apparent loss of Pb from the mixed water is caused by preferential sorption of Ph” to charged sites on the surtaces of suspended particles of minerals, feric hydroxide, and organic matter, These results demonstrate that Pb? tony in river water are strongly nonconservative compared to the uranyl ion( GOs") and Sr ‘The conservative behavior of Sr in solution in the Amazon River is confirmed in Figure 18.20 by the fact that the “'Se/"Sr and US ratios of the Amazon River downstream of Manaus satisfy the linear mixing equation defined by the waters of the Negro and Sofimées Rivers. ‘The point representing the Amazon River lies close to that of the Sofimdes River, meaning that about 90% of the water in the Amazon originates from the Solimdes River The sediment (:-0.2 wm) in suspension in the Solimées and Negro Rivers likewise mixes at the confluence at Manaus. However, the chem- ical composition of the sediment is altered by the preferential deposition of grains of “heavy” minerals and by the pickup of sediment from the bottom of the streams depending on varia- tions in the velocity of the water. In spite of the resulting heterogeneity. the concentrations ofZaire and Amazon Rivers 429 Guyana Shield Lies Pact ean 20 rictwe 8 Drainage basin ofthe Amazon River and its tibutaries: A U = Unucara, N= Negro: § = Solimoes: M-= Madeira. Tj = Tapajos. Adapted from Allegre etal. (1996) assumed to remain constant, the S1-U and Sr-Pb uLAmazon River Water - mixing. lines in. Figure 1821 both indicate. that pe sotmoes |? about 65% of the sediment in the Amazon oso © Jaap River downsteam of Manaus originates fom the a Solimdes River. 20) Ane cop ey tame ba 18,3¢ Model Dates of Sediment. Amazon s Solo k e iver omer 7279 The isotope systematics of Nd and Sr in the Negro amazon sediment in the Amazon River and its tributaries oor0 in Table 18.4 can be used to calculate model dates a with reference to CHUR. Such model dates provide + pob 4 clae to the age of the rocks underlying. the nouke ie Effect of mixing of water of the Grainage basin and thereby identify the provenance Solimées and Negro Rivers at Manaus, Brazil, on of the sediment. the concentrations of Sr, U, and Pb in solution in For example, the Né model date of sediment the Amazon River dowastseam of the coifuence. in the Trombetas River (Table 18.4) is calculated Data rom allege eta (1996), from equation 18.6 0.512638 — 0.19671 — 1) Se, U, and Pb of the sediment in the Amazon River are consistent with mixing of sediment = 0.511500 ~8 092(e" = 1) contributed by the Solimdes and Negro Rivers. In 1.010869 Iv the Sr concentrations of the sediment are 185 Ga430.18, Water and Sediment ‘Amazon River, Water Nagio, « o710 Pf orazo 0.708 + Solimoes | O80 100 150 200 250 (418A «10° ppb * Hue: (s2¢ Isotopic mixing diagram ef Sr in solution in the Solimdes and Negro Rivers. which rmenge at Manaus 10 form the Amazon River. The positon of the point representing the Amazon River downstream of Manaus indicates that about 90% of sts water originates from the Solimbes River, Daa from Allegre etal, (1996 ‘The model dite of Sr in the sediment of the ‘Trombetas River is derived as 0.7045 — O0R161e"" — 1) = 0.74683 ~ 1.6502" = 1 WW.02698 9s Gg raion The Sm-Nd and Rb-Sr model dates af sedi- ment in the Trombetas River ave in agreement and correctly indicate that the sediment ariginates partly from the Precambrian ctaton of Guyana located noni uf the Amon busin. The motel dates of sediment in the rivers listed in Table 185 demon- strate the differences in the geology of the Solimies and Negro Rivers, The model dates of the sed iment in the Solimaes River (Nd: 0.87 Ga, Sr: 0.42 Ga) reflect the presence of mineral particles, derived from the Mesozoic voleanic rocks of the Andes, whereas the model dates of sediment in the Negro (Nd: 1.15 Ga; Sr. 2.71 Ga) are indicative of the Precambrian rocks of the Guyana craton. The Po, pom 50100150200, Si ppm avr 1821 Mixing of suspended sediment in the Solimaes (S) and Negro (N) Rivers at Manaus, Brazil. The deviations of the U and Pb concentrations of sediment in the Amazon River (A) from: the mixing line are attributable 10 selective deposition of the “heavy” mineral fraction and resuspension of sediment from the stream beds, Data from Allegre et al. (1996), ‘Table 18.4, Isotope Ratios of Sr and Nd in ‘Sediment of the Amazon River and Selected ‘Tributaries Rie sere SRW Na ANU Sng ONG Seo 316K OAD —OSLIBS——_O.1N2T Selinger 71819183 GSIZINS NTS Amuss UIST Le OSIRAS ITS ‘elon Marans! Madeira IRS oust Grewa 87283818? 10 Tiombes TUBS 14S STIS 0.020 Tupgos 38540319 Gstine 9.05 Amaron 072186178, SI20BS ONT "Santer Vi Se Se af NBS SR = 710258. ORM, NENG OF De Nd model dates of sediment in the Amazon and Solimoes Rivers in Table 18.5 are older than the Sr model dates. However, the reverse occurs in the Negro and Trombetas RiversTable 18.8. Model Sm-Nd and Rb-Sr Dates Relative to CHUR of Suspended Sediment in the Amazon River below Manaus and in the Solimses and Negro Rivers Zaire and Amazon Rivers 431 ‘Table 18.6. Average Concentrations of U, Th, and Pb and Weighted Average Isotope Ratios of Pb in the Sediment (>0.2 wm) of the Zaire and Amazon Rivers and Their Tributaries Nd Date, Sr Date, River ia Gu Amazon (below Manaus) 0.74 035 Solimies 0.87 0.42 Negro Lis 2m ‘Trombetas 1.65 187 Note: Based on data by Allegre etal. (1996) listed in Table 18.4 18.3 Lead Isotopes, Zaire and Amazon ‘The Pb contained in the sediment transported by rivers resides primarily in grains of K-feldspar and in certain accessory minerals such as 7ircon, apatite, monazite, and so on. In addition, Pb” ions are strongly sorbed by colloidal particles of minerals, by amorphous oxyhydronides of Fe and al and by organic matter. The isotope composition of sorbed Pb is likely to differ from that contained in resistant mineral particles having high U/Pb ratios (e.g. zircon). ‘The average weighted isotope ratios of Pb in sediment of the Zaire and Amazon river systems were used to calculate the abundance of *™Pb and the atomic weights of Pb. These values were used to obtain the average *“UP™Pb and °? THB ratios in Table 18.6. The °°PbP™Pb ratios of bulk sediment (0.2 um) in the Amavon River and its tributaries reported by Allegre et al. (1996) range from 18.67 (Madeira) to 19.95 (Trombetas), and their Pb concentrations vary between 23.5 and 66.3 ppm. However, the ™™*Pb/*+Pb and 1/Pb ratios fof the sediment in these rivers do not define mixing line (not shown), presumably because of the nonconservative behavior of Pb°*. The same statement applies 1© the Zaire River and its tributaries. The *Pb/™Pb and 2" Pbr™Ph ratios of the sediment of the Zaire River and its tributaries loosely define a straight line in Figure 18.22. This Tine cannot be an isochron (or an. errorchron) because the sediment samples are composed of Parameter Zaire Amazon U, ppm 25 (09-43) 3.5 24-43) Theppm = 142 (4.7-19.2) 16.0.(12.5-19.1), 35.6 (246-681) 42.2 (23.5-66.3) 18.746, 19.022 15.742 18.714 39.083 38.997 5.68 457 452 535 265 25.30 Ab®Pb 0.013417 0.013380 At wt Pb 207.2077 207.2023 Sources Allegre etal. 1996, ‘Suspended Sediment, Zaire Sie f and Amazon Rivers pp 15.90 + T 15.80 > 1570 woe tse0/ Zaire: t=2.3 Ga 15.50 1 . 180 «185190195 20.0 209pb/24PD rnouRe 1822 Mixing line defined by the > Pb/"™Pb and ””Pbv""Pb ratios of sediment (0.2 jm) in the Zaire River and its tributaries. ‘Two tributaries of the Amazon River (U = Unucara: T= Trombetas) also fit this array. ‘The isotope ratios of Ph in sediment of the Amazon basin cluster in @ small arca of the diagram, Data from Alléare et al, (1996)43218, Water and Sediment mineral grains having different ages. Instead, the lineacity of this data array is the result of mixing of to principal sediment components containing differing amounts of radiogenic Pb. For example. the sediment may be @ mixture of particles of Precambrian and Phanerozoic ages. The slope of this Ph-Pb array (m = 0.14525) yields a fictitious Ph-Ph date of about 2.3 Ga (Section 10,104). The magnitude of this date implies a Precambrian age for one of the sediment components, ‘The isotope ratios of sediment of the Trombe- (as and Urieara Rivers in the Amazon basin (U and T in Figure 18.22) fit the Pb-Pb array of the rivers in the Zaire basin, The Precambrian provenance of the sediment in the Trombetas River is well estab- lished by their model dates in Table 18.5. Most of the other tributaries of the Amazon River cluster in a small area of 18.3e Implications for Petrogenesis, ‘The sediment being transported by streams from the continents to the oceans accumulates in coastal basins and ultimately forms deposits of marine shale, siltstone, and sandstone. This. sed- iment is representative swith certain imitations of the continental crust. including both Precam- brian basement rocks (granitic gneisses, metavol- canig rocks. ete.) and sedimentary, volcanic, and plutonic igneous rocks of Phanerozoic age, These kinds of rocks collectively contain Sr, Nd, and Pb, whose concentrations and isotope ratios may modify the chemical and isotopic compositions of mantle-derived magmas that intrude the continental crust In addition, a fraction of terrigenous sediment is incorporated into the sediment that accumulates in the abyssal basins of the oceans until it is subducted (e.g.. the Aleutian Trench). Some of the Sr, Nd. and Pb of the subducted sediment is, ansferred 10 the mantle wedge and hence into ‘magmas that form in this envionment. In addition these elements may ultimately reappear in the lavas, of oceanic islands that form above plumes in the underlying mantle, ‘The sediment of the Zaire and Amazon Rivers is connected (0 the EM? magma-souree compo- rent (Table 17.1) in Figure 18.23 by a hyperbotie 19 Sr-Nd, Magma Nd Sources. ya] 1s 05130 - 4e \\3 05125} / ale 05120}- Ae z osits|_1 . 1 1 0700 0.710 0.720 0.730 esi sr over 1824 Relation between the isotope ratios of Sr and Nd of sediment in the Zaire (Z) and Amazon (A) Rivers and their tributaries to the isotope ratios of magma-source components in the mantle: 1 = DMM: 2 = EM: 3 = EM2. 4= HIMU (Table 17.1). Data fom Allegre et al, (1996). mining curve. This diagram therefore illustrates the input of continental Sr and Nd into the petrogenetic processes that operate primarily within the ocean basins. The EM2 component (3 in Figure 18.23) consists of subducted oceanic crust. including ter- rigenous sediment. The crustal imprint is even mote strongly developed when basalt magma from within the mantle-source polygon is contaminated Uirectly by assimilating crustal rocks. represented in Figure 18.23 by sediment of the Zaire (Z) and Amazon (A) Rivers and their tributaries, This kind bof petrogenesis was illusirated in Figure 17.29 by the basalt of the Saddle Mountain Formation of the Columbia River Basalt of Washington and Oregon. Additional examples of assimilation of ‘crustal rocks are the basalts of the Parand plateau of Brazil, the Etendeka Group of Namibia, the Karoo Group of South Africa, the Norilsk area ‘of Siberia, as well as others described by Faure (2001), The isotope ratios of Sr and Pb in the sediment of the Zaire and Amazon Rivers are likewise relatedReferences for Geochemistry of Lakes and Streams (Introduction, Section 18.1 Introduction) — 433 1 EM? by a mixing Tine that appears to be straight (not shown). Therefore, the isotope ratios of Pb of ‘basalt magmas may also be altered by assimilation of crustal rocks, However. the effect is less evident ecause the 2"Ph/ Ph ratios oF crustal rocks (Zaire = 18.746, Amazon = 19.022) are similar to that of EM2 18.4 SUMMARY “The Sr in solution in rivers draining the Precam- brian Shield of Canada is generally enriched in sadiogenic “'St, but the ''Si"Sr ratios of dif ferent rivers range widely depending on the ages and Rb/Sr ratios of the rocks in their drainage basins. The presence of St-rich marine carbonate rocks of Paleozoic age lowers the “'Sr/Sr ratios ‘of streams draining Precambrian rocks. ‘This phe- nomenon indicates that different isotopic varieties ‘of Sr are being mixed in rivers even before the water is discharged into the oceans. Studies of the isotope compositions of Nd and Pb in river water are difficult because of the low concentra tions of these elements at near-neutral values of the pH. In most cases, groundwater ts not in chemical ‘anc isotopic equilibrium with the rocks in which it resides either because insufficient time is available for equilibrium to be established or because of subsurface flow that results in mixing of waters that interacted with different kinds of rocks, In cases where two components of groundwater mix, the “'Sr'Sr and U/Sr ratios form linear mixing arrays TThe isotope compositions of Sr, Nd, and Pb of resistant mineral particles suspended! in streams depend on their ages and parent-daughter ratios, ‘whereas the sorbed fraction of these elements has the same isotope composition as the dissolved fraction. Consequently, the sediment in suspension in rivers contains a record of the ages of the rocks in the drainage basin, whereas the dissolved or sorbed fraction of the clements identifies the minerals that are dissolving in the course of chemical ‘weathering. The difference between the *S1/Sr ratios of sediment and water in the Zaire and Amazon river systems increases with the magnitude of the "'Srf°Sr ratios in the sediment. The "Srf*Sr and 'Nd!“Nd ratios of sediment of both river systems form overlapping data fields in quadrant 1V OF the Sr-Nd isotopic mixing diagram, as expected for rocks of the continental crust Mixing of water and sediment of the Solimdes ‘and Negro Rivers at Manaus, Brazil, can account for the “'Sri"*Sr ratio and the concentrations of Sr and UOs"* in the water of the Amazon River downstream of the confluence. However. Pb? is strongly nonconservative and is removed from solution by sorption to suspended and cal- loidat partictes. ‘The St and Nd mode! dates of sediment in the dributaries of the Amazon River identify the presence of Precambrian basement rocks, espe cially in the Negro and Trombetas rivers, which rain the Guyana Shield north of the Amazon basin, The sediment of the Zaire River and its tributaries defines a straight line in coordinates of SPD PS and "”PRPMPD ratios as a result of mixing of two components of Precambrian and Phanerozoic ages Some of the sediment transported by streams into the oveans is ultimately subducted. The radiogenic isotopes of the subducted terrigenous sediment are partly transferred into the mantle wedge above the subduction zone and can be incorporated into the magmas that are erupted by voleanoes in island ares and coastal mountains (e.g. the Andes). The presence of former terrigenous, sediment in mantle plumes and in oceanic: crust that underplate the continental crust in some places characterizes the EM2 component of magma sources in the mantle REFERENCES FOR GEOCHEMISTRY OF LAKES AND STREAMS (INTRODUCTION, SECTION 18.1 INTRODUCTION) Appelo, C.A.J., and D, Postina, 1993. Genchemistrs Groundwater and Pollution. Balkema, Roterdam, Berner, E. K., and R, A. Berner, 1987. The Global Wazer Cycles Geochemistry and Environment. Prentice Hall, Englewood Cliffs, New Jersey43418, Water and Sediment Berner, E. K., and R.A, Berner, 1996, Globul Environs iment Water, Air. and Geochemical Cycles. Prentice Hal), Upper Saddle River. New Jersey Drever, 11, 1997, The Geochemistry of Natwral Water Surface and Groundwater Environments, xd ed. Prentice-Hall, Upper Saddle River, New Jersey. Faure, G., 1998, Principles and Applications of Gearhem: ‘sory, 2nd ed. Prentice-Hall, Upper Saddle River, New ersey, Feulner, A.J. and J H. Hubble, 1960, Occurrence of srontium in the surface and ground waters of Cham paign County, Ohio. Eron. Geol, $5:176-186. Langmuir, D.. 1997. Aqueous Environmental Geovlhem: isirs. Prentice-Hall, Upper Saddle River, New Jersey. Mori, C., and P. 1. Koeh, 2002, Elevation or alter- ‘tion? Fvaluation of isoopie constraints on paleo- Jatiuides surrounding the Eocene Green River basin, Geology, 342y 151-154 Nest, PL. G. Faure, and W. J, Pegram, 1979, The iso= topie rocks; the Flagstaff Formation of Utah. Sedimentology 26.271 -28, Palmer, MR, and JM. Osenond, 1992. Controls over ‘the Sr isotope composition of river water. Geochim. Cosmochim, Acta, 5620992111 Rhodes, MK. AR Caroll, J.T Pietras, BLL. Beard ‘and C.M. Johnson, 2002. Strontium isotope record ‘of paleohydralogy and continental weathering, Eocene Green River Formation, Wyoming. Geologs, 3012) 167-170. Stumm, W. (Bd), 1990, Aquatic Chemical Kinezes Wiley, New York Stump, W., and J.J. Morgan, 1996. Aquatic Chemistry 3rd ed, Wiley, New York. Wedepohi, K.H., 1978, Handbook of Gevckemistry ‘Sections 37 and 38. Springer-Verlag. Heidelberg, sition of stoatium in nonmarine carbonate REFERENCES FOR RIVERS OF CANADA AND THE WORLD (SECTIONS 18. 1a—18.1b) Faure, G., J. H. Crocker. and P. M. Hurley, 1967, Some aspects of the geochemistry of strontium and calcium in the Hudson Bay and the Great Lakes. Geochim. Cosmuchin, Acta, 3851-401 Faure, G., P.M. Hurley, and H.W. Faichairn, 1963, An ‘estimate of the isotopic composition of strontium in rocks of the Precambrian shield of Noth America. J Geophys. Res, 81B)2323-2329. Faure, G., 1978. Abundance of Sr in comunon igneous rock types. In KH, Wedeyohl (Ed), Handbook of Geochemistry, M4, 98E1-38B4 Krogh, RE, D. W. Davis, and F. Corfu, 1984, Precise U-Pb 2irvon and barkleleyite ages Lor the Sudbury arc In E.G. Pye, A.J. Nabdrett, and P.E, Giblin ‘Eds, The Geology and Ore Deposits ofthe Sudbury Structure, ‘Toronto, Ontario, Ontario Geological Survey. Spex Vol. 1, pp. M28, MeNutt, RH M-Gascoyne, and D.C. Kamineni, 1987 "'SeP°Sr values in groundvaters of the East Bi Lake pluton, Supetior Province, Ontario, Canada. Appr. Geochem,. 293-101 Wadleigh, MA... Veizer, and C. Brooks, 1985, Stron- ‘ium and it isotopes in Canadian rivers: Fluxes ‘and global implications. Geochim, Cosinctiim. Acta, 49:1727-1736, Yang, C. C.Telmer, and f. Veizer, 1986, Chemical dynamics of the St, Lawrence” verine system SDy.9. 3" Op3.5" Cue 6 Syne, and dissolved “SiF S’Sp. Genchim. Comnchin, Acta, 60:881 865, REFERENCES FOR SEDIMENT IN STREAMS (SECTION 18.2) Blum, J.D. Y. Brel, and K. Brown, 199, SihSr ratios of Sierra Nevada stream waters: Implications for relative mineral weathering rates. Gerckion. Cas >mochim. Aeta, S7'S019-S026, Camecon, FM. and K, Hato, 1997. Suomtum and neodymium isotope ratios in the Fraser River, British Columbia: A riverine teansest aeross the Cordileran orogen, Chem, Geol 137 242-283, Douglas. G. B,C. M. Gray. BT. Hart, and R Beckett 1995. A strontium isotopic investigation of the ongin of suspended particulate matter {SPM an the Mures Darling River system, Australia, Geohitn. Cosmechin Aca, 59-3709 3815 Faure, G., 1998. Principles andl Applications of Gece fairs, 2nd ed, Prentice-Hall, Upper Saddle River, New dency Faure, G. 1986, Principles of Isotope Geolox. 2ad ed Wiley. New York, Martin, CE. and M.T. McCulloch, 1999. Nd-Sr iso topic and trave clement yeushemistey of river sedi- iments and soils in fertzed catchment, New South Wales, Austilia. Gevehin: Cosmochion, Acta, 88287 30s, Muffler, L. 1. P.. and B. R. Dee, 1968, Composition and ‘mean age of detritus of the Colorado River delta in the Salon Trough, southeastern California, J. Sed. Petr 38 384-399, Wadleigh, M.A. J. Velzer. and C. Browks, 1985, Siro ‘iui and its isotopes. in Canadi and global implications. Geochim: 49:1727-1736, fers: Fluses ‘osmocthim, ActaReferences for Zaire and Amazon Rivers (Section 18.3) 438 REFERENCES FOR ZAIRE AND AMAZON RIVERS (SECTION 18.3) Allegee, C1, B. Dupré, P. Négrel, and J. Gaillard, 1996. Sr-Nd-Pb isotope systematics me Amazon and Congo River systems: Consiraints about exosion pro esses. Chem, Geol, 131:93-112, Blum, J.D., Y. Brel, and K. Brown, 1993, "SeA*Sr ratios oF Sierra Nevada stream waters: Implications for relative mineral weathering rates. Geochim. Cos machine Acta, ST:SD19-S025, Cameron, F.M,, and. K. Hatori, 1997. Strontium and neodymium isotope ratios in the Fraser River, British Columbia: A rivenne tanseet across the Cordileran ‘orogen. Chem. Geol, 137:243-253, Douglas, G. B., C.M. Gray. BT. Har, and R, Becket. 1995,'A strontium isotopic investigation of the origin ‘of suspended particulate matter (SPMD) in the Murray Darling River system, Australia. Geochim. Cosmochin ‘Acta, $9:3799- 3815 Faure, G., 2001. Origin of fgneous Rovks: the Isoropic Evidence. Springer-Verlag, Heidelberg.