THE ACCUMULATION OF ELECTROLYTES : XI. ACCUMULATION OF NITRATE BY VALONIA AND HALICYSTIS

The nitrate concentration in the sap of Valonia macrophysa, Kütz., is at least 2000 times that of the sea water, and in Halicystis Osterhoutii, Blinks and Blinks, at least 500 times that of the sea water.     

THE ACCUMULATION OF ELECTROLYTES : X. ACCUMULATION OF IODINE BY HALICYSTIS AND VALONIA

Analyses of the sap of Halicystis Osterhoutii and of Valonia macrophysa for iodide indicate accumulations of the order of 1000 to 10,000-fold in the first case, and 40 to 250-fold in the second case. The chemical potential of KI, NaI, HI, and CaI₂ is greater inside than outside.     

THE ACCUMULATION OF ELECTROLYTES : II. SUGGESTIONS AS TO THE NATURE OF ACCUMULATION IN VALONIA

It is suggested that K enters chiefly as KOH, whose thermodynamic potential (proportional to the ionic activity product (a _K) (a _OH)) is greater outside than within. As this difference is maintained by the production of acid in the cell K continues to enter, and reaches a greater concentration inside than outside. KOH combines with a weak organic acid which is exchanged for HCl entering from the sea water (or its anion is exchanged for Cl^-), so that KCl accumulates in the sap. Na enters more slowly and its internal concentration remains below that of K. The facts indicate that penetration is chiefly in molecular form. As the system is not in equilibrium the suggestion is not susceptible of thermodynamic proof but it is useful in predicting the behavior of K, Na, and NH₄.     

THE ACCUMULATION OF ELECTROLYTES : III. BEHAVIOR OF SODIUM,POTASSIUM, AND AMMONIUM IN VALONIA

When 0.001 M NH₄Cl is added to sea water containing Valonia macrophysa there seems to be a rapid penetration of undissociated NH₃ (or NH₄OH) which raises the pH value of the sap so that the thermodynamic potential of KOH becomes greater inside than outside and in consequence K leaves the cell: NaOH continues to go in because its thermodynamic potential is greater outside than inside. NH₄Cl accumulates, reaching a much higher concentration inside than outside. This might be explained on the ground that NH₃, after entering, combines with a weak organic acid produced in the cell whose anion is exchanged for the Cl^- of the sea water, or (more probably) the organic acid is exchanged for HCl.     

THE ACCUMULATION OF ELECTROLYTES : VII. ORGANIC ELECTROLYTES PART 2

Analyses have been made of the inorganic constituents of the juices expressed from the leaves of Rheum, Rumex, and Oxalis. It has been shown that in all cases there is a large excess of inorganic cations over anions in the sap, the average ratio of cations to anions being 3.8 (Part 1, p. 239). The ash analyses of plant tissues (chiefly leaves) reported in the literature have been examined critically, and it has been shown that the preponderance of inorganic cations over inorganic anions in the ash and in the sap is general. It has been concluded that the excess of inorganic cations is consistent with the view that cations pass into the protoplasm chiefly in the form of hydroxides, and are accumulated either in the form of organic salts (such as the oxalates) or in non-polar linkage. It has been concluded that practically all the potassium and sodium found in plant ash must have been present originally in the form of soluble ionogenic compounds, but that a considerable part of the calcium and magnesium may have been present originally in the form of insoluble salts or as components of non-polar compounds. The methods whereby the cations, particularly potassium, may have been accumulated have been discussed, and it has been concluded that as it does not seem very probable that they enter chiefly as nitrates or bicarbonates we may suppose that they go in to a large extent as hydrates: this is highly probable in the case which has been most carefully investigated (Valonia).     

THE ACCUMULATION OF ELECTROLYTES : VII. ORGANIC ELECTROLYTES PART 1

The inorganic constituents of the sap of Rheum (rhubarb), Rumex (field sorrel), and Oxalis (wood sorrel) show a great preponderance of cations over anions, as would be expected if the cations entered chiefly as hydrates (other possibilities will be discussed in Part 2).     

THE ACCUMULATION OF ELECTROLYTES : VI. THE EFFECT OF EXTERNAL pH

It would be natural to suppose that potassium enters Valonia as KCl since it appears in this form in the sap. We find, however, that on this basis we cannot predict the behavior of potassium in any respect. But we can readily do so if we assume that it penetrates chiefly as KOH. We may then say that under normal conditions potassium enters the cell because the ionic activity product (K) (OH) is greater outside than inside. This hypothesis.leads to the following predictions: 1. When the product (K) (OH) becomes greater inside (because the inside concentration of OH^- rises, or the outside concentration of K⁺ or of OH^- falls) potassium should leave the cell, though sodium continues to enter. Previous experiments, and those in this paper, indicate that this is the case. 2. Increasing the pH value of the sea water should increase the rate of entrance of potassium, and vice versa. This appears to be shown by the results described in the present paper. It appears that photosynthesis increases the rate of entrance of potassium by increasing the pH value just outside the protoplasm. In darkness there is little or no growth or absorption of electrolytes. The entrance of potassium by ionic exchange (K⁺ exchanged for H⁺ produced in the cell), the ions passing as such through the protoplasmic surface, does not seem to be important.     

THE STRUCTURE OF THE COLLODION MEMBRANE AND ITS ELECTRICAL BEHAVIOR : IX. WATER UPTAKE AND SWELLING OF COLLODION MEMBRANES IN AQUEOUS SOLUTIONS OF ORGANIC ELECTROLYTES AND NON-ELECTROLYTES

1. Dried collodion membranes are known to swell in water and to the same limited extent also in solutions of strong inorganic electrolytes (Carr and Sollner). The present investigation shows that in solutions of organic electrolytes and non-electrolytes, the swelling of dried collodion membranes is not as uniform, but depends on the nature of the solute. 2. The solutions of typically "hydrophilic" substances, e.g., glycerine, glucose, and citric acid, swell collodion membranes only to the same extent as water and solutions of strong electrolytes. In solutions of typically carbophilic substances (e.g., butyric acid, valeric acid, isobutyl alcohol, valeramide, phenol, and m-nitrophenol) the swelling of the membranes is much stronger than in water, according to the concentration used. For the brand of collodion used the swelling in 0.5 M solution was in some cases as high as 26 per cent of the original volume, as compared to 6 to 7 per cent in water. Therefore, in these solutions the "water-wetted dried" collodion membrane is not rigid, inert, and non-swelling, but behaves as a swelling membrane. 3. The solutes which cause an increased swelling of the membranes are accumulated in the latter, the degree of accumulation being markedly parallel with the degree of their specific swelling action. 4. The anomalously high permeabilities of certain carbophilic organic solutes reported by Michaelis, Collander, and Höber find an explanation in the specific interaction of these substances with collodion. 5. The use of the collodion membrane as a model of the ideal porous membrane is restricted to those instances in which no specific interaction occurs between the solute and the collodion.     

THE UPTAKE OF INORGANIC ELECTROLYTES BY THE CRAYFISH

1. Reasons are given for believing that the uptake of Na⁺, Cl^-, and NaCl by the crayfish occurs through the gills. 2. A crayfish in fresh water, with a Cl concentration of about 0.2 mEq./l., can) by active Cl absorption, compensate entirely for Cl lost in the urine. 3. The carbonic anhydrase activity of the gills is markedly higher than that of other tissues of the crayfish, but the equivalent CO₂ output of the crayfish is far in excess of the equivalent Cl absorption per unit time and weight and thus fails to warrant the supposition that Cl absorption is of respiratory importance. 4. The carbonic anhydrase activity of the soft integument of the lobster, before and after molting, and of the hypodermis of the hard-cuticled animal is almost identical and of the same order as that of other tissues of the lobster. 5. The concentration of the electrolytes was about 7.5 mEq./l.; i.e., considerably lower than in the blood of the crayfish. Cl^- can be taken up independently of the complementary cation. Na₊ can be taken up independently of the complementary anion. K⁺ and SO₄ ⁼ are not taken up at all. In pure NaCl, the Na⁺ and Cl^- are absorbed evidently largely together. Ca⁺⁺ is absorbed only in newly molted animals and in animals preparing to molt but is not absorbed by hard-cuticled animals not preparing to molt. Ca⁺⁺ is taken up independently of Cl^- in pure CaCl₂. 6. Newly molted animals absorb Ca⁺⁺ at a rate exceeding that of the absorption of other absorbable ions (Na⁺ and Cl_-) in the same equivalent concentration. 7. A crayfish utilizes the Ca⁺⁺ in fresh water in the calcification of its cuticle. Since the animal does not swallow water, the Ca⁺⁺ must enter through the exterior. Reasons are given for believing that, unlike Na⁺ and Cl^-, Ca⁺⁺ is absorbed directly from the exterior by the integument and does not enter the body through the gills. 8. During molting, only about 4 per cent of the raw ash and 2.3 per cent of the organic material of the old cuticle is resorbed.