Manganiferous Soil Concretions from Hawaii1

G. P. GLASBY,2 P. C. RANKIN,3 and M. A. MEYLAN 4

ABSTRACT: Manganiferous soil concretions have been located in pineapple and sugar cane plantations ofthe Schofield Plateau, Oahu, and black mangani ferous coatings on the surface of soils have been observed on the crests of embankments next to pineapple plantations on Oahu, Molokai, and Lanai. The concretions and coatings are found inoxisols derived from volcanic parent material. The moisture regime of the soils is characterized by alternate wet and dry periods. This alternation facilitates remobilization and reprecipita tion of manganese and to a much lesser extent iron and associated trace metals in the soils. Optimum conditions for manganiferous soil concretion development are encountered on the Schofield Plateau, where mean annual rainfall exceeds 1000 mm/year but where there is a net evaporation loss from the soils during the dry period (May through October). Remobilization of manganese is less pronounced in the oxisols of Molokai and Lanai, where mean annual rainfall is lower. Thin manganiferous coatings rather than concretions therefore form in these islands. The contents of Mn, Fe, Cu, and Ni of the soils on which Hawaiian con cretions form are higher than those of New Zealand soils in which manganese soil concretions are found. This is reflected by the much redder color of the Hawaiian concretion-bearing soils compared with their New Zealand counter parts. Rare earths show an enrichment sequence: parent rock ---+ soil ---+ soil concretion. A small positive Ce anomaly is noted in the soil and is more marked in the concretions. This may be due to the increasing oxidation of Ce in the concretions relative to the soil, although contamination of the soil by con cretionary material may also playa role. The parent rock shows no Ce anomaly. Barium and Pb are enriched in concretions relative to the surrounding soil, whereas D, Th, Hf, Nb, Zr, and As are present in similar or higher concen trations in the soil relative to the concretions. Arsenic may follow Fe in the soils. Todorokite is the predominant manganese mineral in the Hawaiian soil concretions, not pyrolusite as previously reported. Scanning electron mic roscope studies show the crystalline nature of the manganese oxide minerals in the concretions. CONCRETIONS ENRICHED IN iron and manga the world (Bryan 1952; Childs 1975; Childs nese with respect to surrounding soil material and Leslie 1977; Norrish and Pickering 1977; are relatively common in soils throughout Ross, Franzmeier, and Roth 1976; Sindhu et al. 1977), and the occurrence of man ganiferous and ferruginous concretions in 1 Manuscript accepted 15 October 1978. Hawaiian soils has previously been reported 2 New Zealand Oceanographic Institute, Department of Scientific and Industrial Research, Wellington, New by Patterson (1963, 1971); Sherman (1959); Zealand. Sherman and Kanehiro (1954); Sherman, 3 Soil Bureau, Department of Scientific and Industrial Ikawa, and Matsusaka (1969); Sherman, Research, Lower Hutt, New Zealand. Tom, and Fujimoto (1949); and Walker 4 University ofHawaii, Department ofOceanography, Honolulu, Hawaii 96822. Current address: University (1964). Manganiferous soil concretions have of Wisconsin-Milwaukee, Department of Geological been located in pineapple and sugar cane Sciences, Box 413, Milwaukee, Wisconsin 53201. plantations of the Schofield Plateau, Oahu. 103 104 PACIFIC SCIENCE, Volume 33, January 1979

In addition, black coatings of manganese and 6 to 18 mm on Lanai in the dry season. oxides are seen on the surface of soils on the This would increase to monthly average tops of embankments and on the surfaces values of 125, 100, and 50 to 100 mm, respec of volcanic pebbles exposed above the soils tively, for the rest ofthe year. The reasons for associated with the pineapple plantations. the lack of manganiferous concretions in the Manganiferous and ferruginous deposits soils of the pineapple plantations of Molokai have also been reported in other regions of and Lanai are not known but may be related the Hawaiian Islands. Sherman, Tom, and to the nature of the parent material (i.e., Fujimoto (1949: 120), for example, have re lithology, Mn and Fe contents, redox and ported a thin layer of MnOz around shrub pH characteristics) or, more importantly, roots in Lanai, and ferruginous concretions the hydrological balance (and therefore the have been reported in certain soils from vari leaching and evaporation characteristics) in ous localities on Kauai and Oahu (Sherman the regions in which these soils occur. In this and Kanehiro 1954, Walker 1964). Black paper we report on the geochemistry, min manganese coatings (1 mm or more in eralogy, and mode of formation of man thickness) on weathered basalt and displaying ganiferous soil concretions from the central botryoidal surface textures have also been plateau of Oahu, Hawaii. noted in a 4-m embankment in Kahaluu, Oahu (S. V. Margolis, personal communi cation). From the soil, geological, topographic, SAMPLES and rainfall maps of the islands of Oahu, The concretions and surrounding soil Molokai, and Lanai (College of Tropical sample were collected from a roadside site Agriculture 1971, McCall 1973), it is apparent on route 99 on the Schofield Plateau, Oahu that the pineapple plantations of these three (Figure 1; cf. Macdonald and Kyselka 1967), islands have been established in oxisols at an elevation of approximately 280 m. The (derived from volcanic rock) in areas ofgentle region is one of extensive pineapple and slope. In the Oahu plantations, the soil is sugar cane plantations situated between the Wahiawa Series; in Molokai, Molokai Series; Koolau and Waianae ranges (cf. Macdonald and in Lanai, mainly Molokai and to a and Abbott 1970). lesser extent Lahaina Series (Ruhe et al. 1965, The soil in which these concretions occur United States Department of Agriculture is dark red (2.5YR 3/6) and this constitutes Soil Conservation Service 1972). The parent the upper 2 cm of the soil profile. Below this, rock from which these soils are derived is the soil is very dusky red (lOR 2.5/2). the the Koolau volcanic series on Oahu and the concretions are typically in the range 4 to 9 West Molokai volcanic series on Molokai mm in maximum diameter, ellipsoidal to and Lanai. The plantations are generally at spheroidal with smooth surface texture, and an altitude of 150 to 300 m, extending up to found on or near the surface of the soils. 600 m in Lanai. Rainfall in the region is Internally, the concretions are massive to variable due to the influence of the mountain vaguely concentrically laminated with no ranges on a maritime climate, but in the apparent nuclei. Surface densities of con region of the pineapple plantations the mean cretions larger than 5 mm diameter were annual rainfall is of the order of 1000 mm/ estimated to be up to 600/mz. For analytical year on Oahu, 750 mm/year on Molokai, purposes the two concretion samples are and 500 to 700 mm/year on Lanai. This composites ofconcretions from the same site. compares with a value of6000 mm/year in the The concretions are observed in the soils Koolau Range, Oahu, overlooking the Scho of both the pineapple and sugar cane plan field Plateau. The dry season for these islands tations, but are not distributed throughout is May to October, and monthly rainfall the entire Schofield Plateau. Mulch paper values in the plantations would be of the (asphalt tarred paper) used to be laid just order 25 mm on Oahu, 12 mm on Molokai, beneath the surface ofthe soil in the pineapple Manganiferous Soil Concretions from Hawaii-GLASBY, RANKIN, AND MEYLAN 105

FIGURE I. Schematic diagram showing location of soil concretions on the Schofield Plateau, Oahu, Hawaii plantations to reduce soil moisture loss and (1969) on a Siemens wavelength dispersive to control weeds, although nowadays black XRF. An Fe-micastandard (Flanagan 1973), polythene sheets are used. This sheeting a G-2 standard (Flanagan 1973), and a syn marks the boundary between the two soil thetic mixture (composition similar to man colors noted above. ganiferous concretions) of three standards [BCS 176/1 (Mn ore), BCS 303 (Fe ore sinter), and BCS 269 (firebrick)] were used to assess the accuracy of the analyses as better than ANALYTICAL METHODS 3.5 percent for the major elements. Scanning Electron Microscopy The procedures used were those described Spark-Source Mass Spectrometry in Margolis and Glasby (1973) on a fractured, The samples were prepared as follows: unpolished surface of a concretion. They were ground with an agate mortar and pestle to pass a 50-/lm nylon sieve, added to X-ray Fluorescence Analysis an equal quantity of ultrapure graphite con taining 500 ppm LU Z0 3 internal standard, Major elements in the soil concretions and and thoroughly mixed in a polythene vial. surrounding soil sample were determined Electrodes were formed using a polythylene using the method of Norrish and Hutton die and hydraulic press (Taylor 1965). The 106 PACIFIC SCIENCE, Volume 33, January 1979

FIGURE 2. Scanning electron microscope photograph of fractured internal surface of Hawaiian soil concretion: a, mass of prismatic and tabular crystals (1440 x); b, prismatic and tabular crystals (7500 x); c, hexagonal platelets (3660 x); d, hexagonal platelets on surface of larger prismatic hexagonal crystal (7200 x). electrodes were mounted in an AEI MS702 The mass spectrometric data are con mass spectrograph, and sparked with a radio sidered to have a precision ofbetter than ± 15 frequency voltage of 20 kV at 100 pulses/sec percent. The accuracy of the data is related with a 200 JlS pulse length. Standard Q-2 to the reliability of the standard rock data, photoplates were used to detect the dispersed and also to the presence ofinterfering ions in ion beam. Optical densities ofthe line images the mass spectra. Manganese soil concretions of selected isotopes on the photoplate were can have elevated levels of Ba, and complex measured with a Zeiss densitometer. Isotopes ions of barium carbide can contribute sig of Hf, Yb, Er, Nd, and Ba were used to nificantly to the mass spectrum. The concen determine the Q-2 emulsion response curve trations of elements such as Gd, Tb, and Dy (Taylor 1971). After determination of the could be anomalously high due to the pres average isotope to internal standard ratio ence of interfering ions. Such anomalies can from individual exposures, the element con be observed in the published data for two centrations were obtained from standard New Zealand soil concretions (Rankin and curves derived from the analysis of United Childs 1976). The Arapohue and Waimatenui States Geological Survey, Japanese, and soil concretions have Ba concentrations of South African rock standards. the order of I percent, and the interference

, ..~... ,,,.,,,, .~"·I" .r.... -,." ".... ,..... ,'~ ...... "'._ .... _, ..." pm I

Manganiferous Soil Concretions from Hawaii-GLASBY, RANKIN, AND MEYLAN 107

ions of barium carbide have produced anom TABLE I alously high apparent concentrations for Gd, X-RAY FLUORESCENCE ANALYSIS (%) OF ELEMENTS IN Tb, and Dy. The Hawaiian soil concretions HAWAIIAN SOIL CONCRETIONS AND ADJACENT SOIL studied here have a much lower Ba content (approximately 0.1 percent), and interference CONCRETION I CONCRETION 2 SOIL effects are much reduced. Si02 19.D7 18.89 31.84 AI20 3 26.43 26.19 31.54 Fe20 3 * 9.21 9.24 15.87 MgO 0.66 0.60 0.55 RESULTS CaO 0.23 0.24 0.12 Scanning electron microscope (SEM) Na20 N.A. N.A. N.A. K 20 1.14 1.14 1.68 studies of the concretions show that the MnO 21.33 21.53 1.33 surface is relatively featureless and almost Ti02 1.49 1.51 2.72 smooth, although somewhat grainy. In cross P20S 0.02 0.02 0.09 section at high magnifi~ation, however, the L.O.I. t 17.33 17.50 14.23 Total 96.91 96.86 99.97 fractured internal surface of the concretions CUI 0.33 0.29 0.04 is seen to consist of a mass of euhedral Nil 0.29 0.43 0.04 crystals and interpenetrating twins showing well-defined crystal planes in all directions. NOTE: N.A. = not analyzed. *Total Fe as Fe20). Typically, these crystals are 1.5 Jl long and t L.G.I. weight loss following ignition to lOoooe for 1 he; eu and Ni 0.5 Jl in diameter (Figure 2a, b). Also present were determined on dried sample without ignition. l Copper and Ni data obtained by EDAX X-ray fluorescence spectros to a much lesser extent are hexagonal platelets copy at the University of Hawaii (M. A. Meylan). (Figure 2c). These sometimes grow within a larger crystal (Figure 2d). Each side of these the elongate crystals are in fact only platelets platelets is about 4 Jl long and the platelets on their side. The observations do, however, are about 1 Jl thick. Smaller platelets with agree with the X-ray diffraction data, which sides 0.5 Jl long are also observed. These show the dominant manganese mineral in crystal sizes are large considering the usual the soil concretions to be todorokite. It cryptocrystallinity ofnatural ferromanganese should be noted, however, that Burns (quoted oxide minerals (Johnson and Glasby 1969) in Curtis 1977, p. 371) considers lithio and are the same size range as laminations phorite to be the dominant manganese min in deep-sea nodules [typically in the range eral in these concretions. The reasons for 0.25 to 10 Jl according to Margolis and the well-developed crystallinity of these con Glasby (1973)]. The appearance of masses cretions, compared with deep-sea nodules, of crystals at high magnification under SEM is not understood at present but it may reflect is totally different from the structure of the slow growth rate of these concretions deep-sea manganese nodules where well compared with deep-sea nodules (about 3 developed crystals are rarely observed even mm/106 years) or, more probably, the low on fracture surfaces, although some much Fe/Mn ratio (of the order 0.4) of the con poorer examples have been reported (Brown, cretions. Pabst, and Sawyer 1971; Fewkes 1976, p. 131, The major element composition of the two fig. 49, p. 132, fig. 51; Glasby 1978; Glover concretions and adjacent soil is given in 1977; Xavier 1976). Although no definite Table 1. The Mn contents of the concretions assignment of mineralogy can be made, it is are in general agreement with those previ believed that the elongate crystals are to ously reported by Sherman et al. (1949), and dorokite, whereas the less abundant hexa the soil concretions are seen to display a gonal platelets are birnessite (cL Burns and high Mn/Fe ratio (2.6) and to be enriched Burns 1977). Woo (1973, p. 169, fig. 12), for in Cu and Ni compared to the underlying example, has identified as birnessite hexagon soil. Iron is, however, higher in concentration al platelets that have identical dimensions in the soil than in the concretions. X-ray to those described here. The interpretation diffraction patterns indicate that the con of the SEM pictures may be complicated if cretions contain, in order of apparent abun-

" , 108 PACIFIC SCIENCE, Volume 33, January 1979

TABLE 2 the Hawaii concretions and soil are higher

SPARK-SOURCE MASS SPECTROGRAPHIC ANALYSIS (PPM) than those of their New Zealand counter OF RARE EARTH AND TRACE ELEMENTS IN HAWAIIAN parts (Rankin and Childs 1976). SOIL CONCRETIONS AND ADJACENT SOIL Figure 4 shows the variation ofenrichment factors (concentration in concretion/concen CONCRETION I CONCRETION 2 SOIL tration in surrounding soils) with atomic number. The pattern of REE enrichment is La 54 53 (73) 23 Ce >200 >200 (1,460) 110 similar to that observed in the group 2 soil Pr 21 19 5.9 concretions studied by Rankin and Childs Nd 91 82 (I 19) 23 (1976). Sm 28 25 (34 5.0 Hawaiian soil concretion 2 was analyzed Eu 8.7 7.5 (II) 1.6 Gd 20 16 (20) 4.1 by neutron-activation analysis (P. J. Potts, Tb 2.5 2.4 (3. I) 0.52 personal communic(l.tion). The data are plot Dy 13 12 2.8 ted in Figure 3. Although the absolute REE Ho 2.0 1.8 N.A. concentrations differ from those obtained Er 6.0 4.4 N.A. by mass spectrometry, the shale-normalized Yb 4.6 3.5 (4.8) 1.9 U 2.9 2.9 2.9 patterns are similar. Th 10 10 (10) 12 Table 2 also lists a number of other trace Pb > 100 >100 23 elements determined by spark-source mass Hf 2.8 2.8 (4.5) 4.3 spectrometry. Childs (1975) has previously Ba > 1,000 > 1,000 320 Nb 14 II 2J shown that Ba and Pb are enriched in New Zr 160 130 230 Zealand soil concretions relative to the sur Y 37 33 19 rounding soil. Barium was shown to be As 20 20 >35 largely associated with the Mn-rich phases of the concretions rather than the Fe-rich NOTE: N.A. = not analyzed. Data in parentheses obtained by P. J. Potts and M. SaTre (Open University, England) by neutron-activation phases. The Hawaiian soil nodules are analysis. See Figure 3 for graphical comparison of neutron-activation and mass spectrometric data. markedly enriched in Ba and Pb relative to the surrounding soil. Yttrium is also similarly dance, kaolinite, quartz, gibbsite, hematite, enriched in the Hawaiian soil concretions. and todorokite, whereas the underlying soil The pattern of enrichment of these trace contains quartz, kaolinite, gibbsite, and elements in the Hawaiian concretions relative hematite. The concretions do not contain to underlying soils differs from those of New pyrolusite as previously reported by Sherman Zealand. The elements U, Th, Hf, Nb, and et al. (1949). Zr are present in either similar or higher Table 2 lists the concentration of the rare concentration in the soil relative to the con earth elements (REE) in the two mangani cretions. The depletion of elements that are ferous soil concretions and their surrounding not chemically involved in concretion forma soil. It has become a standard practice to tion in the concretion relative to the soil is normalize REE concentrations in iron-man attributable to the dilution effect, in weight ganese concretions with respect to a standard per weight terms, which occurs when Mn material such as shale (Piper 1974). Figure 3 and Fe oxides precipitate in the pores among shows the distribution ofREE in the analyzed soil particles. samples relative to the mean concentrations in shale (as given by Haskin and Schmitt 1967). Comparison of the rare earth data of DISCUSSION the soils with those of Hawaiian basalts (Schilling and Winchester 1966) shows that The formation of ferromanganese con the rare earths are enriched in the soil (with cretions in soil profiles is well known and is a positive Ce anomaly) relative to their source due to the ability of iron and manganese to rocks. With the exception of the Arapohue change their oxidation states in response to soil concretions, the rare earth contents in Eh andpH changes in the associated naturally = l! _

Manganiferous Soil Concretions from Hawaii-GLASBY, RANKIN, AND MEYLAN 109

...•,

10 '. , . , ., •.... .'. \ . \\...... ~x, . ~.... \,\, .... ,-,.~ ,, "..... ,\ '" , ". \\~ X'""~' ~ ..,. '. ". ,",''x '. .... ~---:". , "'.~ "~on1 --~ 1·0 -0o Concretion 2 Z

Surrounding soil

0·1 La Ce Pr Nd Sm Eu Gd Tb Oy Ho Er Yb

FIGURE 3, Shale-normalized rare earth concentrations for two Hawaiian soil concretions and their surrounding soil. Dotted line refers to neutron-activation analysis data obtained by P, J, PottS and M, Sarre, occurring aqueous system (Childs 1975). In the wetter season ofthe year and precipitation the case of the manganiferous concretions as concretions or coatings during the drier studied here, it seems probable that the for seasons (i.e., conditions of intermediate an mation of the deposits is related to leaching nual rainfall). The more immobile Fe is left ofmanganese from the associated soils during behind in the soil under these conditions. 110 PACIFIC SCIENCE, Volume 33, January 1979 10 , I I .... o I U ~ I ..... c I Q) E I ...c: (J ";:: c J UJ

1·0 ~---.r-----r---r-_---_--r-....,...---,ro---r--_----r---"""-- La Ce Pr Nd 8m Eu Gd Tb Dy Ho Er Yb

FIGURE 4. Rare earth enrichment factors (average concentration in soil concretions/concentration in surrounding soil) for Hawaiian soil concretions.

The higher Mn/Fe ratio of these concretions 1973, Piper 1974, Rankin and Childs 1976). compared to the underlying soils therefore The stabilization of Ce in the 4+ oxidation reflects the more facile migration of Mn com state within the oxidizing environment of pared to Fe in aquebus systems (Krauskopf the concretions is thought to be the cause of 1957). By contrast, ferruginous concretions the marked Ce enrichment with respect to on the Hawaiian Islands are generally found the other REE. The small positive Ce in regions of higher rainfall than on the anomaly exhibited by the surrounding soil Schofield Plateau, Oahu [in excess of 2500 is probably due to microconcretions in the mm/year; Walker (1964)], when manganese soil or "skins" of iron-manganese deposits would be completely leached from the soil on the soil particles. Alternatively, it may and iron mobilized and precipitated. This reflect the increasing oxidation of Ce on situation is reflected in high Fe/Mn ratios of passing from parent rock to soil to soil these ferruginous deposits. concretion. The parent rock shows no Ce The trace element data for the two anomaly (Schilling and Winchester 1966). Hawaiian soil nodules are comparable and Arsenic has been shown to be associated they have a total REE concentration ap with Fe3 + in soil horizons (Goldschmidt proximately six times that in the surrounding 1954). Rankin and Childs (1976) suggested a soil. Iron-manganese concretions are able relationship between As and Fe in New to concentrate and control the distribution Zealand iron-manganese soil concretions. of metal ions in soils (Jenne 1968). Rankin This relationship is also apparent in the and Childs (1976) have shown that REE are Hawaiian soil concretions and their sur associated with Mn enrichment rather than rounding soil. The As concentration in the Fe enrichment in New Zealand soil con surrounding soil is considerably greater than cretions. that in the concretions. Phosphorus, like As, The Hawaiian soil nodules exhibit the occurs in anion form in soil solutions and characteristic positive Ce anomaly found in can be seen (Table 1) to be enriched in the soil and marine manganese nodules (Glasby surrounding soil. Manganiferous Soil Concretions from Hawaii-GLASBY, RANKIN, AND MEYLAN III

Sherman et al. [1949, quoting the data of upper few centimeters of some soils. The Kelley (1912)], have suggested that alternat Mn content ofthe Paaloa soils is 0.06 percent ing wet and dry conditions of the soil are on average (United States Department of essential to the development ofconcretions of Agriculture Soil Conservation Service 1972, "pyrolusite" and "ferruginous-pyrolusite" p. 222, Table 6). Here, the annual rainfall is concretions since they provide the conditions so high that sufficiently dry conditions never for the solution, leaching, oxidation, and develop to facilitate deposition of leached precipitation of the manganese which are manganese. In addition, the Wailua, Wai necessary for the process. According to these pahu, and Ewa soils, which are alluvial authors, "pyrolusite" concretions are not material derived from the Schofield Plateau found in soils that receive sufficient rainfall (Ruhe et al. 1965), contain manganiferous to keep the soil in a moist condition through concretions to a depth of 17 m, Certainly, out the year. enrichment of manganese at such depths From the data presented here, it is sug could not have taken place after deposition gested that the distribution of concretions of the soils. These soils are miPdle to late may be rationalized in terms ofthe hypothesis Pleistocene. Interestingly, the Wahiawa soils put forward by Sherman, Tom, and Fujimoto of the Schofield Plateau display a color (1949). In this, maximum mobilization of change from very dusky red above 30 cm manganese from the soil occurs in the in the soil profile to dark reddis/1-brown Wahiawa soils ofthe Schofield Plateau where below that depth. This color change may mean annual rainfall exceeds 1000 mm/year. reflect the fact that most of the manganese in This high rainfall leads to a lowering of the the upper 30 cm is in the tetravalent state pH, which facilitates transport of manganese but is in the reduced form below that depth. in the soil. The manganese is then deposited Significantly, when this soil is tilled, the as soil concretions during the dry season deeper soil rapidly assumes a darker color. (May to October) when there is a net moisture This is compatible with the idea that maga loss from the soil due to an excess ofevapora nese in the soil is being oxidized to the tion over rainfall. The process ofmobilization tetravalent state on exposure to air. The of manganese is progressively less well de formation of manganiferous coatings on veloped in the oxisols of Molokaiand Lanai oxisols (as on embankments) is also de where the annual rainfall is lower. Thin pendent on the pH~.p.c. of the oxisol, which manganiferous coatings, rather than con has been determined to be in the range 4 to 6 cretions, form in these soils. The changes in (Keng and Uehara 1973). Finally, it should rainfall significantly influence the charac be mentioned that two techniques of pine teristics of the Wahiawa, Molokai, and apple production are used in Hawaii. In the Lahaina Series soils, and the moisture regimes Dole plantations, the pineapple residue is of these oxisols are described as udic, ustic, left on the soil surface as mulch, whereas in or torric depending on precise conditions the Del Monte plantations, the residue is [see McCall (1973) for definition of terms]. burned off, Burning off would influence the The precise mechanism for water loss from amount of organic matter introduced into these soils, and therefore concretion forma the soil and therefore the leaching character tion, may be complex because ofthe complex istics of Mn and Fe in the soil. High organic water-holding capacity of oxisols (Tsuji, content of the soil will facilitate movement Watanabe, and Sakai 1975). Significantly, of Mn and Fe by causing anaerobi~ con the Paaloa Series soils, which are upland ditions during water saturation. soils between the Schofield Plateau and Sherman and Alexander (1959) report that Koolau Range at altitudes of 300 to 520 m the oxisols studied here are similar to the and with an annual rainfall of 1750 to 2250 "red earths" of Australia, Africa, and India mm/year, do not contain manganiferous and are very similar to the Terra Roxas of soil concretions, although perhaps minor Brazil. An interesting test of the hypothesis amounts of manganese oxides occur in the presented here would be to identify the rela- 112 PACIFIC SCIENCE, Volume 33, January 1979 tionship between manganiferous soil con in New Zealand loess, volcanic ash, andesite, cretion formation and rainfall characteristics or limestone (Childs 1975). There is con in these other environments. siderable enrichment of elements during soil One interesting problem is the rate of formation in Hawaii; the Mn and Fe con accretion of these concretions. The oxisols tents of rocks from the Waianae ranges are on which these soil concretions form are on average 0.21 percent and 8.05 percent, generally found on remnants of old geologic respectively (Cross 1915, Macdonald 1940). surfaces (Keng and Uehara 1973), and on From this, it is suggested that the parent Kauai these surfaces have an age of about I material from which Hawaiian soil con million years (Beinroth, Uehara, and Ikawa cretions is derived is generally much higher 1974). However, based on the low content in the transition elements Mn,Fe, Cu, and of eolian-derived quartz in the soils of the Ni than in the New Zealand examples so far Schofield Plateau, Jackson et al. (1971) have studied. In both cases, Mn, Cu, and Ni are suggested that considerable erosion and/or enriched in the concretions relative to the mass wasting of these soils has occurred soil, but in the Hawaiian situation Fe is since their formation in the mid-Pleistocene. depleted in the concretions relative to the The small size of the concretions therefore soil and not enriched as in the New Zealand indicates either a very slow rate of accretion concretions. This suggests a more effective ofthese deposits (somewhat faster than deep fractionation of Mn and Fe in the Hawaiian sea nodules) or, alternatively, periodic dis situation, possibly due to a more complex solution and reformation following tilling transport process involving a cycle of solu or periods of abnormally high rainfall. bilization and precipitation of these elements Agricultural practices in Hawaii are, how during alternate periods of rainfall and ever, too recent to affect significantly the aridity. The Mn and Fe contents in Hawaiian overall mass balance of manganese in soils. soils might suggest th(lt Hawaiian soil con Increased cold frontal rainfall in Hawaii cretions should be more prevalent than their during the last glaciation (P. C. Ekern, per New Zealand equivalents, although this sonal communication; Ruhe 1964; Selling would depend on rainfall and evaporation 1948), for example, may have been sufficient characteristics. Interestingly, soils from pine to prevent concretion formation during this apple plantations are described as being iron period and concretions may therefore post deficient (i.e., deficient in soluble iron) and date the end ofthe last glaciation. ferrous sulfate is used as a fertilizer in this Based on the data of Childs (1975), there region. The extremely high Fe content (15.87 appear.to be several differences between the percent as Fe z0 3 ) of the soil sample studied Hawaiian soil concretions studied here (Table here suggests that at least part of the Fe may I) and New Zealand soil concretions. In be derived from the application of fertilizers. particular, Hawaiian soil concretions are The lower Fe content of the soil concretions characterized by much higher contents of (9.2 percent as Fez0 3), however, suggests Mn, Cu, and Ni and lower contents of Fe that uptake ofthe iron froin the fertilizer into than New Zealand soil concretions. The the concretions has not taken place on any Mn/Fe ratio is also an order of magnitude significant scale. higher in the. Hawaiian concretions. The elements Mn, Fe, Cu, and Ni are all present in higher concentrations in the associated ACKNOWLEDGMENTS Hawaiian soils than in the associated New Zealand soils, but particularly notable is the W. C. Dudley is thanked for providing higher concentration of Fe. These higher logistic support for one of the authors concentrations may be due in part to the (G. P. G.) to travel to Lanai and Molokai. higher contents of these elements in the We also thank P. C. Ekern of the Depart parent rock from which the soils are derived, ments of Water Resources and Agronomy which in Hawaii is dominantly basalt and and Soil Science, University of Hawaii, for Manganiferous Soil Concretions from Hawaii-GLASBY, RANKIN, AND MEYLAN 113

many valuable suggestions. Scanningelectron manganese nodules as determined by tex microscope studies were carried out in the tural and mineralogical analysis. Ph.D. laboratory of S. V. Margolis (University of Thesis. Washington State University, Pull Hawaii), and the help of K. Margolis is man. 169 pp. particularly appreciated. P. J. Potts and M. FLANAGAN, F. J. 1973. 1972 values for inter Sarre of the Open University analyzed one of national geochemical reference samples. the concretions by neutron-activation anal Geochim. Cosmochim. Acta 37: 1189 YSIS. 1200. GLASBY, G. P. 1973. Mechanisms of enrich LITERATURE CITED ment of the rarer elements in marine man ganese nodules. Mar. Chern. 1: 105-125. BEINROTH, F. H., G. UEHARA, and H. IKAWA. ---. 1978. Notes on the surface texture, 1974. Geomorphic relationships of oxisols internal structure and mineralogy of man and ultisols on Kauai, Hawaii. Soil Sci. ganese nodules from the south Penrhyn Soc. Amer. Proc. 38: 128-131. Basin. S. Pac. Mar. Geol. Notes 1(7): 71 BROWN, F. H., A. PABST, and D. L. SAWYER. 80. 1971. Birnessite on colemanite at Boron, GLOVER, E. D. 1977. Characterization of a California. Amer. Mineral. 56: 1057-1064. marine birnessite. Amer. Mineral. 62: 278 BRYAN, W. H. 1952. Soil nodules and their 285. significance. Pages 45-53 in M. F. Glaess GOLDSCHMIDT, V. M. 1954. Geochemistry. ner and E. A. Rudd, eds. Sir Douglas Maw Oxford University Press, Oxford. 730 pp. son anniversary volume contribution to HASKIN, L. A., and R. A. SCHMITT. 1967. geology in honour ofProfessor Sir Douglas Rare earths in shales. Pages 234-258 in Mawson's 70th birthday anniversary pre P. H. Abelson, ed. Researches in Geo sented by colleagues, friends and pupils. chemistry, Vol. 2. John Wiley & Sons, University of Adelaide. 224 pp. New York. BURNS, R. G., and V. M. BURNS. 1977. JACKSON, M. L., T. W. M. LEVELT, J. K. Mineralogy. Pages 185-248 in G. P. SYERS, R. W. REX, R. N. CLAYTON, G. D. Glasby, ed. Marine manganese deposits. SHERMAN, and G. UEHARA. 1971. Geomor Elsevier, Amsterdam. 523 pp. phological relationships of trbpospherical CHILDS, C. W. 1975. Composition of iron ly derived quartz in the soils of the Hawai manganese concretions from some New ian Islands. Soil Sci. Soc. Amer. Proc. 35: Zealand soils. Geoderma 13: 141-152. 515-525. CHILDS, C. W., and D. M. LESLIE. 1977. JENNE, E. A. 1968. Controls of Mn, Fe, Co, Interelement relationships in iron-manga Ni, Cu and Zn concentrations in soils and nese concretions from a catenary sequence water: The significance ofhydrous Mn and of yellow-grey earth soils in loess. Soil Sci. Fe oxides. Adv. Chern. Ser. 73: 337-387. 123: 369-376. JOHNSON, C. E., and G. P. GLASBY. 1969. COLLEGE OF TROPICAL AGRICULTURE/HAWAII Mossbauer Effect determination of parti AGRICULTURAL EXPERIMENT STATION. cle size in microcrystalline iron-manganese 1971. Guide to Hawaii soils. Misc. Publ. nodules. Nature (London) 222: 376-377. 83.32 pp. KELLEY, W. P. 1912. The function and distri CROSS, W. 1915. Lavas of Hawaii and their bution of manganese in plants and soils. relations. Prof. Pap. U.S. Geol. Surv. 88. Hawaii Agr. Exp. Sta. Bull. 26: 42-56. 97 pp. KENG, J. C. W., and G. UEHARA. 1973. CURTIS, C. D. 1977. Sedimentary geochem Chemistry, mineralogy, and taxonomy of istry: Environments and processes dom oxisols and ultisols. Proc. Soil Crop Soc. inated by involvement of an aqueous Florida 33: 119-126. phase. Phil. Trans. Roy. Soc. London KRAUSKOPF, K. B. 1957. Separation of man 286A: 353-372. ganese from iron in sedimentary processes. FEWKES, R. H. 1976. The origin of marine Geochim. Cosmochim. Acta 12:61-84. 114 PACIFIC SCIENCE, Volume 33, January 1979

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TSUJI, G. Y., R. T. WATANABE, and W. S. WOO, C. C. 1973. Scanning electron micro SAKAI. 1975. Influence of soil micro graphs of marine manganese nodules, structure on water characteristics of se marine pebble-sized nodules, and fresh lected Hawaiian soils. Soil Sci. Soc. Amer. water manganese nodules. Pages 165-171 Proc. 39: 28-33. in M. Morgenstein, ed. Papers on the UNITED STATES DEPARTMENT OF AGRICUL origin and distribution of manganese nod TURE SOIL CONSERVATION SERVICE. 1972. ules in the Pacific and prospects for Soil survey of the islands of Kauai, Oahu, exploration. An international symposium Maui, Molokai, and Lanai, State of Ha organized by the Valdivia Manganese waii. U.S. Govt. Printing Office, Washing Exploration Group and the Hawaii In ton, D.C. 232 pp. + 130 maps. stitute of Geophysics, Honolulu, Hawaii, WALKER, J. L. 1964. Pedogenesis of some 23-25 July 1975. 175 pp. high ferruginous formations in Hawaii. XAVIER, A. 1976. Sedimentologische und Hawaii Inst. Geophys. Rept. HIG-64-1O. strukturelle Untersuchungen zur Genese 406 pp. der marinen Eisen-Mangan-Akkretionen ("Manganknollen"). Senckenberg. Marit. 8 :271-309.