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PARTICULATE CARBON AND NITROGEN

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     SUMMARY: Seawater samples are collected at discrete depths 
     in 12-liter Niskin bottles.  The water samples are prefiltered
     (202 µm) and transferred to specially designed, precalibrated
     filtration bottles, pressure filtered through combusted GF/F
     filters and stored frozen for subsequent analysis.  In the
     laboratory, the filters are dried and analyzed for C and N 
     using a Perkin-Elmer model 2400 analyzer. 
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1.  Principle

    Particulate carbon (PC) and particulate nitrogen (PN), including 
both inorganic and organic forms, are present in seawater primarily 
as by-products of biological activity.  Living organisms also contribute 
a variable amount (<1% in deep waters to >50% in the euphotic zone) 
to the total particulate carbon and nitrogen content of seawater.

    Both PC and PN can be measured using commercially-available 
instruments which detect the gaseous by-products of high-temperature 
combustion.  The Perkin-Elmer model 2400 CHN analyzer used in the 
HOT-GOFS project, combines the classical Pregal and Dumas methods 
for the determination of carbon and nitrogen, respectively.  The 
samples are combusted in a pure oxygen environment, the gases mixed 
and separated by frontal chromatography.  The separated gases are 
determined stepwise by a thermal conductivity detector.  


2.  Precautions

     Care must be taken to ensure that contamination with PC and PN 
is avoided.  Samples should, therefore, be kept away from paper, 
wood, food or other carbon-containing compounds.  The filtration 
system that is set up to collect these samples is constructed of 
plastic.  Plastic contains carbon and, therefore, is a potential 
source of contamination.  The carboys and tubing used in this system 
must be kept clean and free of abrading surfaces.  


3.  Sampling, Filtration and Storage

3.1. Seawater samples are collected in 12-liter Niskin bottles and 
     transferred directly to acid-cleaned filtration bottles.  The 
     samples are transferred via Tygon tubing which incorporates an 
     in-line 202 µm Nitex screen prefilter to remove zooplankton or 
     any other rare particles which might otherwise affect the 
     precision of the estimate.  The filtration bottles are 4- and 
     12-liter polyethylene aspirator bottles fitted with a valve 
     assembly and tubing connection.

     Once the rosette sampler is on deck, the vent valve of each 
     Niskin bottle is opened and one end of the drawing tube is 
     attached to the outflow spigot of the sampling bottle and the 
     other end to the tubing connector on the cap of the filtration 
     bottle.  Particular attention is paid to the orientation of 
     the in-line screened drawing tube (the shorter, larger bore 
     section is attached to the Niskin bottle).  The filtration 
     bottle valve is opened and 100-200 ml is run through the 
     transfer tube and valve assembly to rinse the sampling bottle.  
     The bottle and cap are rinsed 3 times in this fashion.  During 
     the rinsing and filling operation, the filtration bottle cap 
     valve is used to control and direct the sample flow.  After 
     rinsing,the cap is placed on the bottle mouth (without 
     tightening), the valve is opened and the polyethylene bottled 
     is filled to the calibration mark.  

3.2. After filling, the filtration bottles are inverted and placed 
     into the filtration rack.  The contents are then pressure 
     filtered (4-7 psi nitrogen gas) through combusted in-line 25 
     mm GF/F filters.

3.3. Following filtration, clean forceps are used to transfer each 
     filter to a clean plastic petri dish containing a 3 cm square 
     piece of combusted foil.  The sample is labeled and stored 
     frozen (-20°C).  Usually only a few ml or less of water remains 
     in the carboy after filtration; this residual water is ignored 
     in assessing the volume filtered unless it appears to be 
     significant compared to the volume of the carboy.  All appropriate 
     data are entered on the data sheet.
  

4.  Analysis

    Standard procedures for instrument warm-up are followed.  Primary 
PC/PN standards are prepared using acetanilide (C8H9NO; mol. wt. = 
135.16).  Standards are made to encompass the range 20-500 ug/sample.  
Blanks are prepared by analyzing combusted GF/F "field filters" and 
the mean value subtracted from the sample value.  Typical ranges in 
analytical blanks, expressed as percentages of the total signal 
produced by a sample in the course of a given analysis, are 5-17% 
for both PC and PN.


5.  Data Reduction and Calculations

    External standard data are used to prepare a standard curve of C 
(or N) versus corrected signal counts, and linear regression statistics 
are calculated.  An EXCEL spreadsheet is used to calculate PC and PN 
(µg l-1) for each sample based on standard curve, corrected signal 
counts and volume of seawater filtered.


6.  Precision and Accuracy

    Replicate samples are routinely analyzed to estimate the precision 
of our PC and PN analyses.  The average coefficients of variation for 
such replicate analyses are 12% and 10%, respectively.  Accuracy is 
estimated from determinations of the C and N contents of reference 
standards analyzed along with samples during each analytical run.  
This accuracy, expressed as the mean percent difference between the 
analytical determination and the known C and N contents of the 
standards, is found to be 6% for PC and 13% for PN.  Note that the 
estimates of accuracy apply only to standards containing >10 µg N 
and >70 µg C.  Below these levels, we have found the performance of 
the PE-2400 to be suspect.  Therefore sample volumes large enough 
to keep above this lower limit are used.


7.  Equipment/Supplies

    PE-2400 (or equivalent) Carbon/Nitrogen analyzer with integrator
    Cahn (or equivalent) electronic balance
    combusted 2.5 cm GF/F filters (450°C, 4 hours)
    ethanol-cleaned forceps for handling filters
    combusted foil (450°C, 4 hours)
    aluminum foil for covering work area
    clean petri dishes
    low pressure filtration apparatus (4-7 psi)
    valved polyethylene aspirator bottles


8.  Reagents

    acetanilide standard


9.  References

    Sharp, J. H.  1974.  Improved analysis for particulate organic 
    carbon and nitrogen from seawater. Limnology and Oceanography, 19, 
    984-989.