You are on page 1of 3





and a suspension of resin in water poured into an ion exchange column ( 8 x 0.5 cm), After settling, it was washed with three 50-ml portions of distilled water. Tnvestigation of cobalt and zinc adsorbed from seawater onto the resin column Samples ( 1 and 5 liters) of filtered seawater (0.5 Jo) at its natural pH were equilibrated with several ,Gi of either carrier-free zinc-65 or carrier-free cobalt-60 and allowed to flow down individual resin columns. Retention of the ions was estimated by examining the eluate for activity; both cobalt and zinc were completely retained by the resin from both the 1 and 5 liter samples of seawater. Elution of the adsorbed elements

recovery of zinc was increased from 60% to 75%.


Each column was washed with two 20ml portions of distilled water to remove residual seawater. Dilute hydrochloric acid (0.2 N) was then passed down each column and the eluate monitored for radioactivity. Both cobalt and zinc were released from the resin column, a volume of 100 ml being necessary for complete removal of the cobalt but only 60% of the original zinc. On repeating the elution using 100 ml of 0.2 N sulfuric acid, the

This preliminary investigation has demonstrated the use of the reagent bromooxine, supported on a resin column, as an effective method for concentrating trace amounts of cobalt and zinc from seawater. Using a small volume of dilute sulfuric acid, it is possible to elute all of the cobalt and 75% of the zinc off the column. This column, when suitably washed with distilled water, can be reused for further concentration steps. This method has the added advantage that the seawater does not have to be specially treated prior to the concentration stage. G. TOPPING Department of Civil Engineering, University of Strathclyde, Glasgow, Scotland.

CARRITT, D. E. 1953. Separation and concentration of trace metals from natural waters. Anal. Chem., 25: 1927-1928. Marine geochemistry : Some 1964. -a Grad. Sch. R.I., guesses and gadgets. Oceanogr., Narragansett Mar. Lab., Occas. Publ. 3(1965), p. 203-211. RILEY, J. P., AND G. TOPPING. 1969. The use of 5,7-dibromo-Shydroxyquinoline for the concentration of certain trace elements from sea water. Anal. Chim. Acta, 44: 234-236.

DETERMINATION OF AMMONIA IN NATURAL WATERS PHENOLHYPOCHLORITE METHODS The blue color of indophenol obtained by the reaction at high pH of ammonia, phenol, and hypochlorite has been studied by several workers. Berthelot reported the reaction for the first time in 1859. Since then many modifications have been tried. Applications of this method to the direct determination of ammonia in seawater have failed because of the interference of magnesium and calcium ions, but Riley ( 1953) used the reaction for the analysis
This research was fully Atomic Energy Commission ( 11-1) GEN 10, P.A. 20. supported Contract by U.S. No. AT



of ammonia in distillates of seawater. Although his procedure is reproducible and sensitive, it has the disadvantage of requiring distillation. Newell ( 1967) developed a method using chloramine-T instead of hypochlorite to produce the blue indopheno1 color with ammonia. His method is lengthy and involves extraction of the color by n-hexanol. Emmet (1968) produced the blue indophenol color after buffering the solution at pH 9.5. This method, although reproducible, has poor sensitivity and requires extreme attention to detail for its success. The procedure presented here





again uses a high pH but eliminates interference due to precipitation by complexing magnesium and calcium with citrate. No distillation or extraction is necessary and a batch of determinations can be completed within an hour. Working conditions are not critical and there is no interference from other trivalent forms of nitrogen. For the last reason, the approach may be preferable to the Richards and Kletsch ( 1964) method despite its lower sensitivity.

The following reagents were prepared using water freshly removed from an ion exchange resin column in the hydrogen form. 1) Phenol-alcohol solution. Dissolve 10 g of reagent grade phenol in 100 ml of 95% v/v ethyl alcohol USP. 2) Sodium nitroprusside 0.5%. Dissolve 1 g of sodium nitroprusside in 200 ml of water. Store in an amber bottle for not more than one month. 3) Alkaline solution. Dissolve 100 g of trisodium citrate and 5 g of sodium hydroxide in 500 ml of water. 4) Sodium hypochlorite solution. Use a solution of commercial hypochlorite (e.g., Chlorox) which should be at least 1.5 N. The solution slowly decomposes and its strength should be checked periodically. 5) Oxidizing solution. Mix 100 ml of sodium citrate solution and 25 ml of hypochlorite solution and use the same day. For natural waters, the procedure consists of the successive addition of 2 ml of phenol solution, 2 ml of sodium nitroprusside solution, and 5 ml of oxidizing reagent to 50 ml of sample, mixing thoroughly after each addition. The color is allowed to develop at room temperature (22-27C) for 1 hr and the absorbance recorded at 6,400 A in a spectrophotometer with a lo-cm length cuvette. All the glassware used must be cleaned by washing initially with warm dilute hydrochloric acid and rinsing thoroughly with distilled water. Sodium nitroprusside at a concentration of 0.5% is sufficient to catalyze the reaction and produce a stable and low blank. The

absorbance of samples is unchanged for at least 24 hr. A higher concentration produces a high and unstable blank which increases with time. Twenty-five milliliters of the hypochlorite solution (Chlorox) in 100 ml of sodium citrate solution was sufficient for the oxidation to be completed in 1 hr in both freshwater and seawater. The addition of reagents as indicated above gave the best results. At high pH values, the reaction is faster but a slight blue coloration (not due to the presence of ammonium compounds but associated with the presence of nitroprusside ) is suppressed when working with distilled water. This results in an unrepresentatively low blank and an erroneously high value for the ammonia content of seawater. At the pH used in the current technique (9.8 in seawater and 10.4 in distilled water), the blue color from the nitroprusside is formed equally in both samples and blanks and the development time for the color is not unreasonably long. If hydrogen sulfide is present, it must first be removed by acidifying solutions to pH 3 with dilute hydrochloric acid and passing air vigorously until no more sulfide smell is noticed. The sensitivity of the method is identical in freshwater and seawater so that either can be used for calibration; distilled water was used for blanks.

Samples of different concentrations of ammonia in freshwater and filtered seawater were analyzed and Beers law was obeyed in the concentration range from 0.1 to 10 pg-atoms N/liter. With lo-cm cuvettes, the blank absorbance was 0.05 and a factor of 6.5 related absorbance to concentration ( in lug-atoms N/liter ) . The standard deviation of a set of samples containing a concentration of 3 pgatoms NH,-N/liter was 0.07 pg-atom N/ liter. Solutions of amino acids and of urea in seawater were added to seawater to the extent of 3 pg-atoms N/liter. Negligible responses were obtained, the absorbancies


reaction. Nav. Ship Res.

being equivalent to less than 0.1 pug-atom N/liter of ammonia, from glycine, alanine, lysine, histidine, arginine, tyrosine, glutamic acid, and urea. No color resulted from the addition of nucleic acids.


NEwFLl& Cent*y Rep* 2570* 1967. The determination of am. . monia in sea water. J. Marine Biol. Assoc.
U.K.. 47: 271-280. RICHARDS: F. A., AND R. A. KLETSCH. 1964. The spectrophotometric determination of ammoma and labile amino compounds in fresh and seawater by oxidation to nitrite, p. 65-81. In Y. Miyake and T. Koyama [eds.], Recent researches in the fields of hydrosphere, atmosphere, and nuclear geochemistry. Maruzen Co., Tokyo. RILEY, J. P. 1953. The spectrophotometric determination of ammonia in natural water, with particular reference to sea water. Anal. Chim. Acta, 9: 575-589.

Institute of Marine Resources, University of California, San Diego, La Jolla 92037.

EMMET, R. T. 1968. Direct spectrophotometric analysis of ammonia in natural water by the






The rate of consumption of dissolved oxygen from overlying water by undisturbed sediments is a rapid and sensitive index of benthic community metabolism. In sediments covered with well-aerated water, reducing substances in the surface layers are rapidly oxidized; oxygen is also consumed by the organisms within the benthic community. Oxygen consumption by a benthic community is the net result of these two processes. Many studies of benthic oxygen uptake have been carried out with different types of aquatic sediments using a variety of techniques, and the importance of various factors affecting oxygen consumption by undisturbed sediments has been considered (Edwards and Rolley 1965 ) . Although previous workers have noted the importance of temperature to oxygen uptake in individual benthic communities (Edwards and Rolley 1965; Carey 1967; Pamatmat 196S), the widespread importance of this factor has not Despite the variety of been recognized. environments considered, the logarithm of sediment oxygen uptake is significantly correlated with the logarithm of temperature ( Fig. 1). Only measurements on sediment covered with water in short-term ( l-3 hr ) experiments are included in the regression calculation. -~
1 Issued as Canadian International Program Contribution No. 37. Biological

To consider the effect of temperature on oxygen uptake by the benthic community in Marion Lake, British Columbia (Efford 1967)) sediment cores (20 cm2, 5 to 6 cm deep) were taken in glass cylinders with minimum distortion of the sediment surface. The upper portion of the cylinders contained water that originally overlaid the sediment, and the ends of the cylinders were sealed with rubber stoppers. Dissolved oxygen in water overlying the sediment was measured before and after incubation by a micro-Winkler technique (Fox and Wingfield 1938). The standard error of 12 determinations with replicate sediment cores was *lo%, while variation between aliquots taken from the same sample for oxygen determination was 23%. Marion Lake is low in total dissolved solids ( >15 mg/liter), so no modification of the standard Winkler technique was required. All changes in the concentration of dissolved oxygen were due to biological activity within the sediment; there were no significant changes in dissolved oxygen in water-filled cylinders without sediment or over sediment treated with 10% neutralized formalin. Sediment cores from various depths (O-5 m ) in the lake were incubated in the dark at in situ temperatures at least once a month during 1968. The relationship between temperature and sediment oxygen uptake is shown in Fig. 2. The slope of