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PRIMARY PRODUCTIVITY

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     SUMMARY:  The 14C-radiotracer method is used to measure 
     the assimilation of dissolved inorganic carbon (DIC) by 
     phytoplankton as an estimate of the rate of photosynthetic 
     production of organic matter in the euphotic zone.
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1.  Principle

    The 14C method, originally proposed by Steeman-Nielsen (1952), 
is used to estimate the uptake of dissolved inorganic carbon (DIC) 
by planktonic algae in the water column.  The method is based on the 
fact that the biological uptake of 14C-labeled DIC is proportional 
to the biological uptake of 12C-DIC.  If one knows the initial 
concentration of DIC in a water sample, the amount of 14C-DIC added, 
the 14C retained in particulate organic matter (14C-POC) at the end 
of the incubation and the metabolic discrimination between the two 
isotopes of carbon (i.e., 5% discrimination against the heavier 14C 
isotope), then it is possible to estimate the total uptake of carbon 
from the following relationship:

                              DIC * 14C-POC * 1.05
                C uptake  =   --------------------
                                  14C-DIC added 

    Due to the potentially toxic effects of trace metals on phytoplankton 
metabolism in oligotrophic waters, the following procedure is used to 
minimize the contact between water samples and possible sources of 
contamination.


2.  Cleaning

2.1. HCl (Baker Instra-Analyzed) solution (1M) is prepared with high 
     purity hydrochloric acid and freshly-prepared glass distilled 
     deionized water (DDW).

2.2. 500 ml polycarbonate bottles are rinsed twice with 1M HCl 
     (Baker Instra-Analyzed) and left overnight filled with the same 
     acid solution.  The acid is removed by rinsing the bottles three 
     times with DDW before air drying.

2.3. Go-Flo bottles, fitted with teflon-coated springs, are rinsed 
     three times with 1M HCl and DDW before use.

2.4. Pipette tips used in the preparation of the isotope stock and 
     in the inoculation of samples are rinsed three times with 
     concentrated HCl (Baker Instra-Analyzed), three times with DDW 
     and once with the sodium carbonate solution (Chapter 14, section 
     3.2) and stored in a clean polyethylene glove until used.


3.  Isotope Stock

3.1. The preparation of the isotope stock is performed wearing 
     polyethylene gloves.  A 25 ml acid-washed teflon bottle and a 
     50 ml acid-washed polypropylene centifuge tube are rinsed three 
     times with DDW.
3.2. 0.032 g of anhydrous Na2CO3 (ALDRICH 20,442-0, 99.999% purity) 
     are dissolved in 50 ml DDW in the centrifuge tube to provide 
     a solution of 6 mmol Na2CO3 per liter.

3.3. 3.5 ml of NaH-14CO3 (53 mCi mmol-1; Research Products Inc.) 
     are mixed with 16.5 ml of the above prepared Na2CO3 solution 
     in the teflon bottle.

3.4. The new stock activity is checked by counting triplicate 10 µl 
     samples with 1 ml β-phenethylamine in 10 ml Aquasol-II.

3.5. Triplicate 10 µl stock samples are also acidified with 1 ml of 
     2 M HCl, mixed intermittently for 1-2 hours and counted in 10  
     ml Aquasol-II to confirm that there is no 14C-organic carbon 
     contamination.  The acidification is done under the hood.  
     The acidified dpm should be <0.001% of the total dpm of the 14C 
     preparation.


4.  Incubation Systems

    Typically we measure primary production using in situ incubation 
techniques.

4.1. A free-floating array equipped with VHF radio and strobe light 
     is used for the in situ incubations.  Incubation bottles are 
     attached to a horizontal polycarbonate spreader bar which is 
     then attached to the 200 m, 1/2" polypropylene in situ line at 
     the depths corresponding to the sample collections. 

4.2. Generally eight incubation depths are selected (5-175 m, 
     approximately).


5.  Sampling

5.1. Approximately 3 hours before local sunrise, seawater samples 
     are collected with acid- washed, 12-liter Go-Flo bottles using 
     Kevlar line, metal-free sheave, teflon messengers and a 
     stainless steel bottom weight.  A dedicated hydrowinch is used 
     for the primary productivity sampling procedures in a further 
     effort to reduce/eliminate all sources of trace metal contamination.

5.2. Under low light conditions, water samples are transferred to the 
     incubation bottles (500 ml polycarbonate bottles) and stored in 
     the dark.  Polyethylene gloves are worn during sample collection 
     and inoculation procedures.  No drawing tubes are used.


6.  Isotope Addition and Sample Incubation

6.1. Three light bottles, three dark bottles and 1 time-zero control 
     (see Chapter 14, section 8) are collected at each depth for in 
     situ incubation.  In situ dark bottles are deployed in specially-
     designed, double-layered cloth bags with VelcroR closures.

6.2. After all water samples have been drawn from the appropriate Go-Flo 
     bottles, 250 µl of the 14C-sodium carbonate stock solution is added 
     to each sample using a specially-cleaned pipette tip. The samples 
     are deployed before dawn on a free-floating, drifter buoy array.

6.3. At local sunset, the free-floating array is recovered and all in 
     situ bottles are immediately placed in the dark and processed as 
     soon as possible. The time of recovery is recorded. 


7.  Filtration

7.1. Filtration of the samples is done under low light conditions and 
     begins as soon as the incubation bottles are recovered from the 
     in situ array.

7.2. 200 µl are removed and placed into a second LSC vial containing 
     0.5 ml of β-phenethylamine.  This sample is used for the 
     determination of total radioactivity in each sample.

7.3. The remainder is filtered through a 25 mm diameter GF/F filters.  
     The filters are placed into prelabelled, clean glass liquid 
     scintillation counting vials (LSC vials) and stored at -20 °C.


8.  14C Sample Processing

8.1. One ml of 2 M HCl is added to each sample vial (under the hood).  
     Vials are covered with their respective caps and shaken in a 
     vortex mixer for at least 1 hour with venting at 20 minute 
     intervals.  To vent, the vials are removed from the shaker, 
     and the cap opened (under the hood).  After shaking is completed, 
     the vials are left open to vent under the hood for an additional 
     24 hours.

8.2. Ten ml of Aquasol-II are added per vial (including vials for total 
     14C radioactivity) and the samples are counted in a liquid 
     scintillation counter.  Samples are counted again after 2 and 
     4 weeks, before discarding.  Counts have shown a consistent 
     increase during the first two weeks and become stable between 
     the second and the fourth week.  This is probably the result of 
     sample hydrolysis or diffusion of radioactivity from the GF/F 
     filter matrix, thereby reducing the extent of self-absorption.  
     Only the 4-week count is used for 14C calculations.  Counts per 
     min (CPM) are converted to disintegration per min (DPM) using 
     the channels ratio program supplied by the the manufacturer 
     (Packard Instrument Co.).


9.  Calculations

    From the data derived above we can estimate several properties of 
the phytoplankton populations at Station ALOHA.  Total daylight organic 
carbon production is calculated from the 12-hour uptake data (after 
corrections for 12-hour dark activities).  Net daily organic carbon 
production is calculated from the 24-hour light/dark samples (corrected 
for the time-zero blank activities).  Phytoplankton population respiration 
is taken as the difference between the 12-hour light and the 24-hour 
light/dark incubations.  Net primary production is used as the estimate 
of phytoplankton carbon production for the purposes of comparison to 
other ecosystem-level processes (e.g., standing stock assessments, 
vertical C-flux, etc.). 


10.  Equipment/Supplies

     Go-Flo bottles
     kevlar hydroline
     teflon messengers
     stainless steel weight
     temperature- and light-controlled deck incubation system 
       (NORDA/USM incubation system)
     free-drifting productivity array (including polypro line, 
       spreader bars, surface floats, buoy, radio 
     transmitter and strobe le light)
     500 ml wide-mouth polycarbonate bottles
     vacuum filtration system
     liquid scintillation counting (LSC) vials 
     pipettes
     glassware 
     vortex mixer
     liquid scintillation counter (Packard model 4640; United 
       Technologies Inc.)


11.  Reagents

     distilled deionized water (DDW)
     HCl for trace metal analysis (Baker Instra-Analyzed)
     Na2CO3 (99.999%)
     NaH-14CO3 solution (cat #CMM-50, Research Products Inc.)
     β-phenethylamine
     Aquasol-II (Dupont)
     2 M HCl


12.  References

     Steeman-Nielsen, E.  1952.  The use of radioactive carbon (14C) 
     for measuring organic production in the sea.  Journal du Conseil, 
     18, 117-140.