NOTES

107

COLORIMETRIC DETERMINATION
ABST-RACI In the reducing environment of anoxic basins manganese (III) or (IV) is reduced to soluble Mn ( II ) ; the deep waters of the Black Sea contain up to 500 cLg Mn ( II ) / liter, about 100 times the oceanic average. When this manganese was measured with formaldoxime, color development was erratic if the reagents were added separately. Rapid and reproducible color development was achieved by using a mixed ammonia/formaldoxime reagent added singly to the sample. Precipitation was avoided by maintaining the pH in the range 8.8-8.9. No interferences from sulfide or dissolved salts were observed. A small correction was made for interference due to iron. Dissolved manganese values in the Black Sea ranged from a midwater maximum of ca. 460 ,ug Mn/liter to ca. 250 pg/ liter in deep water.

OF

MANGANESE IN ANOXIC WATERS~

Determination of the low levels of manganese in oceanic waters normally requires a concentration step in the analytical procedure, such as coprecipitation with ferric hydroxide (Rona et al. 1960) or magnesium hydroxide ( Koroleff 1947)) or solvent extraction with diethydithiocarbamate into chloroform (Rona et al. 1962) or ammonium pyrollidine dithiocarbamate into methyl isobutyl ketone (Morris 1968). Recently ion exchange has also been used (Riley and Taylor 1968). For the higher levels of manganese found in the deep waters of the Black Sea it should be possible to carry out the analysis without the necessity of a concentration step, and we examined procedures for this. We attempted direct measurement of the sample by atomic absorption spectroscopy using a Perkin Elmer model 303 instrument fitted with a three-slot burner head and using an air acetylene flame. The manufacturers claim a detection limit of 5 pg Mn/liter for the instrument for aqueous solutions, however, the salinity of the sample ( 18-23%~) prevented this limit being achieved both by clogging the burner and aspirator and by light scattering in the flame. We found a detection limit of about 50 ,ug/liter and judged the method at that level to be insufficiently precise for small variations in the manganese content of these waters. Methods in which the manganese is oxidized to permanganate by persulfate or periodate are characterized by poor sensitivity and by chloride interferences, and these methods were not investigated further. The most attractive possibility seemed to be the use of a formaldoxime method (Morgan and Stumm 1965; Henriksen 1966). In this procedure manganese reacts with formaldoxime (formaldehyde oxime) in alkaline solution to form an intense orange red. The sensitivity of the method is about 5 times that of the permanganate methods. But there are several disadvantages. Iron interferes by forming a similar

The chemistry of manganese in natural waters is complex. In oxygenated waters manganese probably exists in its higher oxidation states, Mn( III) or Mn ( IV), and its solubility will be limited by equilibria with 6 MnOz. In a reducing environment, characterized by the presence of H& such as occurs in stagnant basins, manganese is reduced to Mn( II ) and can accumulate in the dissolved form to a significantly greater extent. In our recent investigation of the chemistry of Black Sea waters, precise analyses for dissolved manganese were required; this paper reports the development of a suitable method. The manganese content of seawater generally lies in the range 0.5-3 pg/liter (Riley 1965). However, in the reducing conditions of the deep water of the Black Sea values of 200-500 pg/liter have been reported (Mokyevskaya 1961). This increase of about loo-fold over normal oceanic levels has been attributed to the surface input of insoluble particles of Mn02 from rivers with reduction and dissolution of these particles at depth after sinking through the halocline and into the anoxic waters.
1 Contribution No. 1825 from the Woods Hole Oceanographic Institution. This work supported by AEC Contract AT(30-I)-4150 and NSF Grant GA-1659.

108

NOTES

colored complex. Precipitation of alkaline earth hydroxides may occur under the alkaline conditions necessary and, according to Morgan and Stumm ( 1965)) dissolved oxygen must be present for the color to form. This last criterion is of special interest in the analysis of anoxic waters. In spite of these difficulties we investigated the formaldoxime method further.
EXPERIMENTAL

Reagents Formaldoxime-dissolve 20.0 g of hydroxylamine hydrochloride in 450 ml od distilled water. Add 10 ml of formaldehyde solution (37%) and make up to 500 ml with distilled water. Ammonium hydroxide-sp gr 0.90. Manganous manganese standard-dissolve 0.2876 g of potassium permanganate in 100 ml of distilled water. Add 3 ml of concentrated sulfuric acid then sulfurous acid (SOs/water) dropwise until the color disappears. Boil the solution gently to rid it of excess sulfur dioxide, cool, and make up to 1 liter with distilled water. The solution contains 100 pg Mn/ml. Procedure Adjustment of pH Morgan and Stumm ( 1965) found maximum color intensity of the manganese formaldoxime complex at pH 9.2. Under these conditions precipitation of calcium and magnesium hydroxides may occur with seawater samples. An investigation of the maximum pH attainable before precipitation in our samples showed that at 8.8-8.9 color development was complete and no precipitation occurred. Effect of hydrogen sulfide

of sulfur, which interfered with the colorimetric reaction. Oxidation with Hz02 produced a similar precipitate, moreover peroxide itself adversely affected color development. We used a column of amalgamated cadmium filings to remove sulfide as insoluble mercury and cadmium sulfides, but this too proved inefficient. A careful study of the results showed that the time taken between addition of the formaldoxime reagent and the raising of the pH was an important factor, suggesting destruction of the formaldoxime reagent by sulfide attack. We also observed this phenomenon in certain samples free of sulfide and stored in polyethylene, suggesting attack by organics leached from the container. Once formed, the manganese-formaldoxime complex seemed stable in the presence of sulfide, and to facilitate rapid formation of this complex we made up a combined ammonia-formaldoxime reagent. Adding this reagent to the sample caused immediate color formation even in the presence of up to 500 pgatom H,S-S/liter and in samples stored in polyethylene. Color stability Color development took place in a few seconds and was stable for 30 min, after which time it slowly increased. In practice, measurements were made within 5 min of mixing of sample and reagent. Interferences The principal interference is that of iron which forms a pink complex with the formaldoxime reagent. Goto et al. (1962) have shown that this complex can be destroyed by the addition of EDTA and hydroxylamine hydrochloride. Henriksen (1966) found that at concentrations of iron below 1 mg/liter the complex was still incompletely destroyed; he recommended adding extra iron to the sample. The amount of dissolved iron in Black Sea waters varies between 0.5 and 50 pg/liter (in preparation). In our experience the color due to this quantity of iron was not completely removed by the addi-

Since dissolved oxygen and sulfide are mutually exclusive, the presence of H2S in the samples caused us concern. Our preliminary attempts at analysis resulted in weak and erratic color development and we tried to remove the sulfide. Bubbling the sample with air or oxygen was tedious and gave a white precipitate, presumably

NOTES

109 atom SiO,--Si/liter, providing that the pH of the final solution was low enough to prevent precipitation. Method Seawater samples had been acidified to a pH of 2.0 at the time of collection; the reagent used was adjusted to bring the pH of the final solution to 8.8. Pretreatment of the samples was unnecessary. We pipetted 35.0 ml of seawater into a 125-ml erlenmeyer flask, swirled it, and added 3.0 ml of a mixed reagent containing formaldoxime and ammonia in the ratio of 5: 2. We then measured the color in a lo-cm cell at 450 nm between 2 and 30 min after mixing. The method was calibrated by adding 1 ml of a standard manganese solution containing 10 pg Mn/ml to 34.0 ml of a seawater sample low in manganese. Effect of salinity The salinity of the sample has no effect on the method up to a level of 35%0. Reproducibility and detection limit

TABLE

1.

Effect

of iron

on the determination manganese

Absorbance

of

Sample

Seawater Seawater Seawater Seawater Seawater Seawater

+ 10 pg Mn + 20 pg Mn + 10 pg Mn + 1.0 ,ug Fe + 20 pg Mn + 2.0 pg Fe

0.007 0.521 1.031 0.007 0.531 1.054

tion of EDTA and hydroxylamine and, since iron analyses were available for all our samples, a simple correction factor ( <3%) was applied to the data. Table 1 shows the effect of iron on the analysis as determined by the addition of known quantities of iron to a surface sample. Henriksen (1966) has further reported that phosphate in the presence of calcium causes a significant interference. Black Sea waters have abnormally high concentrations of phosphate and silicate, so this effect was investigated. The intensity of the color was not reduced in the presence of 8 pug-atom PO h3--P/liter and 100 rugTABLE 2. Determinations of dtisolued manganese at seZected stations in the Black Sea. Cruise Atlantis II 49, March-April 1969
Dissolved oxygen (ml/liter) Dissolved sulfide (,ugatom S/liter) Dissolved manganw.e (/.&liter)

We checked the reproducibility of our method by a series of duplicate analyses; at a level of 300 pg Mn/liter it was 3.5%. The detection limit is 10 pug Mn/liter.
RESULTS

Station 90 110 130 150 170 190 Station 10 150 500 1,000 1,500 2,150 Station 75 250 750 1,250 2,,000

1444 (43 49 N, 31 o 41 E) 6.88 2.38 0.17 0.02 1462 (43 7.5 10.0 23.8 9.9 10.5 6.8 169 387 448

Table 2 reports data from three stations; these confirm the observation of Mokyevskaya ( 1961) that the maximum concentration is found in midwater close to the oxygen-hydrogen sulfide transition zone. We are grateful to Mr. C. L. Smith for his excellent assistance in the laboratory. P. G. BREWER D. W. SPENCER Woods Hole Oceanographic Institution, Woods Hole, Massachusetts 02543
REFERENCES

01 N, 33 03 E) 23.3 33.1 319 369 380 12.8 454 314 269 259 263

q
1463 (43 0.16 z -

00 N, 33 59 E) 69.0 275 401 456 38.0 427 298 264 256

GOTO, K., T. KOMATSU, AND T. FURUKAWA. 1962. Rapid calorimetric determination of manganese in waters containing iron. Anal. Chim. Acta 27: 331-334. HENRIKSEN, A. 1966. An automatic modified formaldoxime method for determining low

110

NOTES RILEY, J. P. 1965. Analytical chemistry of seaIn J. P. Riley and G. water, p. 295-424. Skirrow [eds.], Chemical oceanography, v. 2. Academic. AND D. TAYLOR. 1968. Chelating resin; for the concentration of trace elements from sea-water and their analytical use in conjunction with atomic adsorption spectrophotometry. Anal. Chim. Acta 40: 479-

concentrations of manganese in water containing iron. Analyst 91: 647-651. KOROLEFF, F. 1947. Determination of manganese in natural waters. Acta Chem. Stand.

1, 503-506.

MOKYEVSKAYA, V. V. 1961. Manganese in waters of the Black Sea. Proc. Acad. Sci. USSR, Chem. Technol. Sect. (English Transl.)

137: 1445-1447.

MORGAN, J. J., AND W. ST~MM. 1965. Analytical chemistry of aqueous manganese. J. Amer. Water Works Ass. 57: 107-119. deterMORRIS, A. W. 1968. The simultaneous mination of vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc in sea-water by X-ray fluorescence spectrometry. Anal. Chim. Acta 42: 397-406.

485.
RONA, E., L. K. AKENS, L. MUSE, AND D. W. HOOD. 1960. Texas Agr. Mech. Coll., Contrib. Oceanogr. Meteorol. 5. -, D. W. HOOD, L. MUSE, AND B. BUGLTO. 1962. Activation analysis of manganese and zinc in sea water. Limnol. Oceanogr. 7: 201-206.

SEDIMENT PROFILE CAMERA FOR ZN SZTU STUDY OF ORGANISM-SEDIMENT RELATIONS~

ABsTRAm An instrument is described that will take high resolution photographs of silt-clay bottom types in profile. The bottom (lo-20 cm) is penetrated by a slowly descending ( <7 cm/set) wedge-shaped Plexiglas chamber, and the sediment profile that is cut is photographed. Such photographs reveal in situ details of bottom topography, sediment texture, depth of bioturbation, biogenic_ structures, and living positions of mud-dwelling benthos. The instrument can be modified to take closeup vertical photographs of the bottom and to obtain undisturbed core samples.

INTRODUCTION

Sedimentologic and ecologic studies of fine-grained ( silt-clay) bottoms frequently require techniques of in situ observation The texture and water and sampling. content of the surface of subtidal muds are significantly controlled by organismsediment interactions taking place in the upper few centimeters of the bottom (Rhoads and Young 1970). Conventional samplers such as free-fall corers or grabs generate a pressure wave that can wash away unconsolidated surface sediment and organisms before a sample is taken and are therefore inadequate for careful study of
1 Part of this study was supported by National Science Foundation Grant GB-7181 and the U.S. Office of Naval Research.

muds with a high content of water; SCUBA diving is inefficient in water deeper than 20 m when several stations must be taken. Problems of in situ observation and detail sampling prompted us to design a ship-deployed instrument to take sediment-water profile photographs and closeup vertical photographs and to obtain undisturbed core samples of bottom muds. We wish to thank Mr. F. Nutley for assisting us with many of the design details of this instrument; he also did all of the machining and assembled the apparatus. The camera was tested and used at sea aboard the Marine Biological Laboratory (Woods Hole, Mass.) vessel RV A. E. Verrill. We wish to thank Capt. P. Graham for his help. We also wish to thank Dr. R. Gordon and M. Ruggiero for their advice and assistance.
DESCRIPTION

Sediment profile

camera

Figure 1 shows the instrument rigged to obtain sediment-profile photographs. The apparatus consists of one moving part (exclusive of the camera), the cradle, supported by a rigid pipe frame and connected to the winch cable by a piston. The cradle can be moved up and down by producing tension or slack on the