﻿CRUISE REPORT: AR07W
(Updated MAY 2015)






Highlights







                          Cruise Summary Information

               Section Designation  AR07W (aka: HUDSON2014007)
Expedition designation (ExpoCodes)  18HU20140502; 18HU14007 (ISDM format) 
                  Chief Scientists  Igor Yashayaev / BIO
                             Dates  2014 MAY 02 - 2014 MAY 24
                              Ship  CCGS HUDSON 
                     Ports of call  Dartmouth, NS, Canada 

                                                61° N
   Geographic Boundaries (approx.)  65° W                    48° W
                                                37° N

                          Stations  44
      Floats and drifters deployed  0
    Moorings deployed or recovered  2 recovered, 4 deployed

                              Contact Information:

                                 Igor Yashayaev
          Ocean Sciences Division • Department of Fisheries and Oceans
                       Bedford Institute of Oceanography
                  PO Box 1006 Dartmouth, NS, Canada • B2Y 2A4
                          Igor.Yashayaev@dfo-mpo.gc.ca



















                                  CRUISE REPORT

                                  HUDSON 2014007

                                   LABRADOR SEA,
                                  WOCE LINE AR07W
                              Extended Halifax Line

                               May 2 – May 24, 2014








A. CRUISE NARRATIVE 

1. Highlights 

a. WOCE Designation:         WOCE Line AR07W & Extended Halifax Line 

b. Expedition Designation:   HUD2014007 or 18HU14007 (ISDM format) 

c. Chief Scientist:          Igor Yashayaev 
                             Ocean Sciences Division 
                             Department of Fisheries and Oceans 
                             Bedford Institute of Oceanography 
                             PO Box 1006 
                             Dartmouth, NS, Canada B2Y 2A4 
                             Igor.Yashayaev@dfo-mpo.gc.ca 

d. Ship:                     CCGS HUDSON 

e. Ports of Call:            May 02, 2014, BIO, Dartmouth, NS, Canada 

                             May 24, 2014, BIO, Dartmouth, NS, Canada 

f. Cruise Dates:             May 02 to May 24, 2014 





2. Cruise Summary Information 

a. Cruise Track 

A cruise track is shown in Figure A.2.1. The ship's position at 0000 UTC on 
each day of the cruise is indicated with a date label. 

The World Ocean Circulation Experiment (WOCE) - format cruise station summary 
file (SUM) outlines the science operations conducted during the cruise. 


Figure A.2.1: Cruise track for HUD2014007. The yellow dots indicate the ship’s 
              position for each hour of the voyage. The red dots and date 
              labels indicate the ship's position at 0000 UTC for that 
              particular date. 

Figure A.2.2: Cruise track for HUD2014007 with CTD stations, mooring locations 
              and Argo float deployment site. The pink line indicates the 
              outbound track and the light-blue line indicates the inbound 
              track. 


b. Total Number of Stations Occupied 

The CTD / ROS station positions are shown in Figure A.2.2. Table A.2.1 lists 
the science operations for HUD2014007. 

Along AR07W, the stations were full-depth WHP small volume rosette casts with 
up to 24 rosette bottles. Water samples were analyzed for CFC-12, SF6, total 
inorganic carbon (TIC), total alkalinity, oxygen, salinity, nutrients (nitrate, 
phosphate, and silicate), pH, and bacterial abundance. Chlorophyll was analyzed 
at depths less than 200m at most stations. Samples were collected for 129I 
(iodine-129) and O-18 (Oxygen-18) on selected casts. 


Table A.2.1: Science operations conducted on HUD2014007. 

 Cast    Number of               Operation                          Operation 
 Type    Operations               Details                            Numbers 
-------  ----------  ---------------------------------  ----------------------------------
Rosette     44           26 of the 28 regular AR07W              see Table A.2.2 
 & CTD                 sites (L3 line) were occupied.
                       Sites 1 and 2 could not be oc-
                        cupied because of ice cover. 
                        Extra occupations included: 
                     7.5, 8.5, 9.5, 10.5, 11.5, 11.51, 
                       12.5, 13.5, 14.5, 16.5, 17.5, 
                       19.5, 22.5, 23.5, 24.5, 25.5, 
                                26.5, 27.5 

           1             Bedford Basin Test Station                     1 

          26               Halifax Line sites:            4, 172, 173, 174, 176, 178, 180, 
                                                        182, 184, 186, 188, 190, 192, 193, 
                                                        199, 200, 201, 202, 203, 205, 207, 
                                                             208, 211, 214, 217, 220 

           2                   Other Casts                         16, 160 

           9                  Biology Casts             9, 17, 33, 47, 86, 120, 150, 157,       
                                                                     165 

           7                  Aborted Casts             28, 76, 167, 169, 170, 171, 196 

  MVP      5            Moving Vessel Profiler Tows         13, 149, 154, 161, 166 

Moorings   2                    Recovery                           135, 140 
           5                   Deployment                   6, 10, 12, 36, 136 
           3                 Release Tests                         5, 11, 35 

 COPS     11                                            19, 20, 34, 49, 50, 69, 87, 88, 
                                                              139, 153, 162 

Oblique    9                                            18, 48, 68, 89, 97, 121, 138, 151, 
Profiler                                                             152 

Biology   42              200 micron net tows            See Table A.4.2.1. for occupation  
                                                                   locations 
          30              76 micron net tows             See Table A.4.2.1. for occupation 
                                                                   locations 
           9             Egg Production rates            See Table A.4.2.1. for occupation 
                                                                   locations 
          14                   Multinet                  See Table A.4.2.1. for occupation 
                                                                   locations 
           1             Oblique Ring Net tow                         92 



Table A.2.2: AR07W (L3) sites with rosette / CTD operation numbers for 
             HUD2014007.

                             AR0W      2014007 Deep Cast
                          Site Number  Operation Number 
                          -----------  -----------------
                              1              - 
                              2              - 
                              3             129 
                              4             125 
                              5             122 
                              6             117 
                              7             113 
                              7.5           130 
                              8             110 
                              8.5           131 
                              9             134 
                              9.5           137 
                             10             109 
                             10.5           147 
                             11             108 
                             11.5           144 
                             11.51          107 
                             12             106 
                             12.5           105 
                             13             104 
                             13.5           103 
                             14             102 
                             14.5           101 
                             15              25 
                             16              29 
                             16.5            96 
                             17              37 
                             17.5            93 
                             18              40 
                             19              43 
                             19.5            91 
                             20              51 
                             21              54 
                             22              90 
                             22.5            55 
                             23              58 
                             23.5            82 
                             24              81 
                             24.5            78 
                             25              77 
                             25.5            59 
                             26              73 
                             26.5            70 
                             27              62 
                             27.5            67 
                             28              65 
 

Figure A.2.2: HUD2014007 locations (red-filled stars) for operations involving 
              one or more of the following data collection methods: Rosette, 
              CTD and LADCP. 


Stations along the AR07W Labrador Sea section and station HL_02 of the Halifax 
Section (HL) were occupied during the mission. 


c. Floats and Drifters deployed 

No floats or drifters were deployed. 


d. Moorings deployed or recovered 

The Aanderaa current meter mooring near station L3_08 on the AR7W line was once 
again recovered on May XX, 2014. Mooring #1824 was recovered successfully under 
good sea conditions. A new mooring was deployed in the central deep channel of 
the Labrador Sea – the North Atlantic Mid-Ocean Channel (NAMOC) at location 
XXX, depth XXX, date XXX. The replacement mooring #1844 was deployed 
successfully on May XX, 2014. These moorings were both in the water for X days 
for comparison. (Did we do the same overlap in 2014?) Two other mooring – one 
at 2900 m on the Labrador side – was recovered successfully. That deep Labrador 
Slope mooring was not replaced. 

Three Amar acoustic moorings for Hilary Moors-Murphy were deployed near the 
Gully area to monitor whale activity. (please update this) 


Recoveries: 

M 1823   55º 33.4968’ N   Standard mooring consisting of one current meter and 
         53º 41.1712’ W   two Microcats. It was positioned within the Labrador 
                          Sea on the Labrador Slope for a 12-month deployment 
                          at 2756 metres. 

M 1824   55º 07.1844’ N   Standard mooring consisting of one current meter and 
         54º 05.5209’ W   one microcat. It was positioned within the Labrador 
                          Sea on the Labrador Slope for a 12-month deployment 
                          at 1034 metres. 


Deployments: 

                          NAMOC mooring 

M 1844   55º 06.8651’ N   Standard mooring consisting of one current meter and 
         54º 05.2361’ W   two Microcats. It was positioned in the Labrador Sea 
                          on the Labrador Slope for a 12-month deployment at 
                          about 1000 metres. 
M 1849   43º 51.7349’ N   Amar mooring MidGul at 1580 meters (Middle of Gully). 
         58º 54.5984’ W 

M 1850   43º 51.8254’ N   Amar mooring GulSho at 1583 meters (halfway between 
         58º 35.2911’ W   the Gully and Shortland canyons). 

M 1851   44º 05.8633’ N   Amar mooring ShoHald at 1545 meters (halfway between 
         58º 03.3814’ W   Shortland and Haldimand canyons). 



A software package called M-Cal (Mooring Calibrator) V 1.04 was used. M-Cal is 
a subset of a program called WorkBoat by James Illman of Software Engineering 
Associates. This enables the user to position the mooring once on the bottom. A 
computer is linked to the ship’s navigation as well as, in this case, to the 
Benthos DS7000 deck unit. As the ship travels near the mooring, M-Cal 
transponds to the acoustic release and measures the time interval between the 
send and reply pulses. This information combined with the navigation data 
enables the program to calculate the position of the release. As more and more 
data is gathered, the position continually updates. M-Cal also calculates a 
depth for the release. 

This software is of great use if a mooring is off location for some reason. M-
Cal gives a position so that locating the mooring is much quicker. Transponding 
to a release only gives a slant range and not a direction. A ship has to 
randomly travel to minimize this slant range which could be time consuming. 


Figure A.2.3: HUD2014007 mooring deployment locations (pink-filled diamonds) 
              and mooring recovery locations (blue-filled circles). 



3. List of Principal Investigators 

Table A.3.1. List of Principal Investigators; see Section 7 for addresses. 

Name                 Affiliation                      Responsibility 
-------------------  -------------------------------  -------------------------
Kumiko Azetsu-Scott  BIO                              Chemistry program 
                     Azetsu-ScottK@mar.dfo-mpo.gc.ca  coordination, TA, TIC, 
                                                      CFC-12, O18, SF6, and pH. 

Erica Head           BIO                              Biological program 
                     HeadE@mar.dfo-mpo.gc.ca          coordination, 
                                                      Macrozooplankton 
                                                      distribution, abundance, 
                                                      and metabolism 

Bill Li              BIO                              Pico-plankton 
                     LiB@mar.dfo-mpo.gc.ca            distribution and 
                                                      abundance, bacterial 
                                                      abundance and 
                                                      productivity 

John Smith           BIO                              Radioisotope sampling
                     SmithJN@mar.dfo-mpo.gc.ca        program 

Igor Yashayaev       BIO                              Senior Scientist,
                     YashayaevI@mar.dfo-mpo.gc.ca     hydrography, Argo and 
                                                      mooring program 
                                                      coordination 



4.1  Physical - Chemical Program 

a. Narrative 

The physical and chemical program on HUDSON 2014007 continued an annual series 
of measurements in the Labrador Sea that began in 1990 as a contribution to the 
World Climate Research Programme and has evolved into a component of a 
multidisciplinary regional monitoring effort. The broad goals are to 
investigate inter-annual and long-term changes in the physical and chemical 
properties of the Labrador Sea and better understand the mechanisms that cause 
these changes. A particular focus is on changes in the intensity of winter 
overturning of surface and intermediate-depth waters and the resulting 
formation of Labrador Sea Water with varying temperature and salinity 
properties. This overturning is part of the thermohaline circulation that plays 
a role in the global climate system. Convection also transfers atmospheric 
gases such as oxygen and carbon dioxide from the surface layers to intermediate 
depths. The resulting oceanic storage of anthropogenic carbon reduces the rate 
of increase of carbon dioxide in the atmosphere but also increases the acidity 
of oceanic waters. 

An occupation of the extended Halifax Line (when feasible) crossing the Scotian 
shelf, slope and in so-called Slope Water region complements the study of the 
Labrador Sea and is seen as an important part of the offshore monitoring 
program. In the 2014 mission we occupied the longest ever version of this line 
(CTD, water sampling at all stations and multinet tows at all deep stations and 
shallow net tows over the shelf). As a result we crossed the same Gulf Stream 
meander three times and sampled Antarctic Bottom Water providing a good 
reference for transient tracer measurements. 

We recovered two moorings over the continental slopes off Labrador (at about 
1000 m and 2900 m isobaths) and redeployed the shallower on the Labrador Slope 
and one in the central trench (NAMOC – see below). 

The physical-chemical investigations are part of a larger multidisciplinary 
effort seeking a better understanding of interannual and long-term changes in 
regional ecosystems. 


HUDSON 2014007 program elements included: 

 1. CTD profile measurements of pressure, temperature, salinity, dissolved 
    oxygen, pH, fluorescence, and light intensity at a fixed set of stations 
    (AR07W/L3 line) spanning the Labrador Sea from Hamilton Bank on the Labrador 
    Shelf to Cape Desolation Island on the West Greenland Shelf; 

 2. XHL – please insert from 2013 report 

 3. Measurements of salinity, dissolved oxygen, nutrients (nitrate/nitrite, 
    phosphate, silicate), CFC-12, SF6, dissolved inorganic carbon, alkalinity 
    and Iodine-129 from discrete water samples from a rosette sampler on the CTD 
    package; 

 4. Recovery and redeployment of a current meter mooring providing near-bottom 
    current and temperature measurements on the Labrador Slope in 1000 m water 
    depth; 

 5. Recovery of one current meter moorings at 2900 m isobath on the western and 
    eastern ends of AR07W; 

 6. Deployment of a mooring in the NAMOC. 

 7. Current measurements at CTD stations from a Lowered Acoustic Doppler Current 
    Profiler (LADCP) and Electromagnetic (EM) current meter; 

 8. Temperature profile measurements from eXpendable BathyThermographs (XBTs) at 
    selected points between CTD stations (not done in the 2014007, but we 
    mention this to reflect XBT as a part of the program); 

 9. Autonomous float deployments as part of the Canadian Argo Program and the 
    international Argo Project; 

10. MVP 

11. Physical and chemical measurements on station HL2 of the Halifax Line on 
    the Scotian Shelf in support of the Atlantic Zone Monitoring Program 
    (AZMP); 

12. A phytoplankton biomass/primary productivity program conducted; 

13. A microbial program; 

14. A mesozooplankton program. 


The Labrador Sea and Extended Halifax Line (XHL) station work went well except 
for problems with CTD cable termination on the Extended Halifax Line. Eight 
additional stations were conducted on the Labrador Sea (western) side and ten 
on the Greenland (eastern) side of AR07W. Due to ice conditions the two inshore 
stations on the Labrador Shelf were not occupied during this mission. 

MVP was towed in transit to the AR7W line and between AR7W and XHL but shortly 
after passing the continental slope on the way to XHL, the cable got separated 
from the drum of the MVP winch and lost with the sensor package due to 
instrumental failure. 


b. Chemical Oceanography 

The chemistry program conducted in the GP Lab during HUD2014007 included 
analysing water samples for total dissolved inorganic carbon (TIC), total 
alkalinity (TA), transient tracers (CFC-12 and SF6), nutrients, and dissolved 
oxygen. Water samples for pH and oxygen isotope composition were also 
collected, preserved, and stored for later analysis. 


c. Radioisotope Sampling Program 

Water samples were collected for 129I from a near surface rosette bottle at 12 
stations on the L3 (AR07W) line. Fuller depth sampling for 129I was carried out 
on four L3 stations. See table A.2.1 for the list of corresponding operation 
numbers. 



4.2 Biological Program 


a. Biological Oceanographic Sampling Program 
   Jeff Anning and Tim Perry 

Nearly all stations occupied were sampled for a number of biological 
parameters. In the upper 100 m samples were collected for chlorophyll analysis 
and at the surface samples were taken to measure particulate organic carbon, 
and determine pigment composition by HPLC and absorption spectra. At all 
stations duplicate phytoplankton samples, integrated over the upper 50 m., were 
preserved with Lugol’s and formalin. 


b. Zooplankton Sampling 
   Marc Ringuette / Erica Head 

The zooplankton sampling is part of an ongoing program, the aim of which is to 
investigate the distribution, abundance and life history of the major 
zooplankton groups found in the Labrador Sea and its associated shelf systems. 
Particular emphasis is placed on the copepod species of the Calanus genus, 
which dominate the zooplankton in this region. 

We occupied a total of 51 stations where we performed a grand total of 108 net 
hauls. Vertical tows were taken on the way out of Halifax harbour at HL_02, at 
3 stations in transit to the AR7W line, at 26 stations on the AR7W line, at 3 
stations in transit to the to the Halifax Extended Line (HXL) line including 
Station 27 off St-John’s and at 18 stations on the extended Halifax Line). At 
all stations, tows were made from 100 meters to the surface using a ring net of 
75 cm in diameter and 200 μm mesh size, except on the Halifax Line and station 
27 where tows were from 1000 m or bottom. Additional tows were made using a 
using a 30 cm 76 μm mesh ring net at 42 stations. See Table A.4.2.1 for 
details. 


c. Egg Production rates (EPr) of Calanus finmarchicus in the Labrador Sea 
   Marc Ringuette / Erica Head 

EPr was measured at 12 different stations with the primary goal being to 
measure the secondary production of the predominant copepod species of the 
Labrador Sea. The number of eggs laid during the 24 hours following capture 
allows estimation of the egg production females would have had in-situ on a 
daily basis. 

Ongoing work on summarizing egg production rates of Calanus finmarchicus 
throughout the entire North Atlantic Ocean led us to believe that a part of the 
generally observed high variability may be due to methodological discrepancies. 
We therefore evaluated the rates with set-ups regularly used by other 
laboratories: all methods sharing attempts to try to avoid cannibalism as much 
as possible. Three different treatments were used. For two Large Petri dishes 
(LP), 90mm in diameter were used and for one Large Volume chambers LV (>300ml 
volume) with funnels and mesh inserts at the bottom were used. For each 
treatment 20 females were put into individual vessels. For one of the LP 
treatments and the LV treatment females were incubated for 24 hours. For the 
second LP treatment, eggs were removed and counted every 6 hours and eggs 
spawned during the first 6 hour interval were kept aside (LP*6hrs) and 
recounted at the end of the 24 hour incubations. Comparisons of the 3 methods 
were done at 9 stations in the Labrador Sea. See Table A.4.2.2 for details. 


d. Depth Distribution of Calanus finmarchicus in the Slope Water off the 
   Scotian Shelf 
   Marc Ringuette / Erica Head 

The vertical depth distribution of Calanus finmarchicus in the Slope Water off 
the Scotian Shelf was investigated at 14 stations, from HL_20, in the Gulf 
Stream, to HL_06 at the Scotian Shelf shelf break. Five depth strata (1000-800, 
800-600, 600-400, 400-200, 200-0 meters) were sampled using a square 0.5 x 0.5 
m multi-net fitted with 200μm mesh nets. See Table A.4.2.1 below. 


e. Euphausiid EtOH samples 
   Marc Ringuette / Erica Head 

A 1 m diameter ring net fitted with a 500 μm mesh was lowered to ~100 m at 
Station L3_18A and then hauled in at a rate of ~ 1 m s-1 as the ship proceeded 
at a speed of 1.5 knots, giving an oblique tow. This procedure was designed to 
catch euphausiids, which are less abundant and more mobile than most 
zooplankton forms. At another station (L3_10.5), euphausiids were observed to 
be quite abundant in one of the routine vertical 200 μm mesh net tows. An extra 
tow was done at this station for the specific purpose of collecting 
euphausiids. These 2 samples were preserved in EtOH 95% for genetic analysis, 
to be carried out by colleagues at the University of Connecticutt. 

 
Table A.4.2.1: List of net tows carried out on Labrador Sea monitoring mission 
               HUD2014007. 

                                              Ring Net 
         Station           Date   Multi-net  200μm  76μm  EPr/Livebugs 
         ----------------  -----  ---------  -----  ----  ------------
         HL2               2 May                      X        X 
         MIDGULLY          3 May                      X  
         NFLD Shelf        5 May                      X  
         Transit SWLS      6 May                      X  
         L3_15                                        X        X 
         L3_16             7 May                      X        X 
         L3_17                                        X        X 
         L3_18                                        X        X 
         L3_19             8 May                      X        X 
         L3_20                                        X        X 
         L3_21                                        X        X 
         L3_23             9 May                      X        X 
         L3_27                                        X        X 
         L3_28                                        X        X 
         L3_27.5 
         L3_26                                        X        X 
         L3_25                                        X        X 
         L3_24            10 May                      X        X 
         L3_22                                        X        X 
         L3_18A           11 May               X 
         L3_16.5                                      X       X 
         L3_14.5                                      X       X 
         L3_07            13 May                      X       X 
         L3_06                                        X       X 
         L3_05                                        X       X 
         L3_04                                        X       X 
         L3_03                                        X       X 
         L3_09            14 May                      X       X 
         L3_11.51                                     X       X 
         L3_10.5          15 May                      X       X 
         NFLShelf BIO/O2  16 May                      X 
         STN27                                        X       X 
         Off Grand Banks  17 May                      X 
         HL_20            19 May      X 
         HL_18            20 May      X 
         HL_17                        X 
         HL_16                        X 
         HL_15            21 May      X 
         HL_14                        X 
         HL_13                        X 
         HL_12                        X 
         HL_11            22 May      X 
         HL_02             2 May                      X       X 
         MIDGULLY          3 May                      X 
         NFLD Shelf        5 May                      X 
         Transit SWLS      6 May                      X 
         L3_15                                        X       X 
         L3_16             7 May                      X       X 
         HL_10            22 May      X 
         HL_09                        X 
         HL_07                        X        X 
         HL_08                        X 
         HL_06            23 May      X        X 
         HL_05                                 X       X 
         HL_04                                 X       X 
         HL_03            24 May               X       X 
         HL_02                                 X       X 
 

Table A.4.2.2: Egg production rates experiments during HUD2014007 cruise in the 
               Labrador Sea. 

                    Station          LP*6hrs  LP*24hrs  LV*24 
                    ---------------  -------  --------  -----
                    MIDGully            X        X        X 
                    NFLD Shelf          X        X        X 
                    Transit SWLS        X        X        X 
                    L3-17                        X      
                    L3-20               X        X        X 
                    L3-27.5                      X      
                    L3-22               X        X        X 
                    L3-14.5             X        X        X 
                    L3-06               X        X        X 
                    L3-11.51            X        X        X 
                    NFLShelf BIO-O2     X        X        X 
                    Off Grand Banks              X      


Figure A.4.2.1: HUD2014007 Ring net tows (pink-filled squares) and multi-net 
                tows (green-filled diamonds) locations. 


e. Primary Production Measurements 
   Jeff Anning 

Water samples for photosynthesis-irradiance (P-I) experiments were collected 
from the rosette at the surface and 30m at 7 stations. For each incubation 
experiment, 33 aliquots were inoculated with 14C labelled sodium bicarbonate 
and then incubated at in situ temperatures at 30 light levels (+ 3 dark 
bottles) for approximately 3 hours. At the end of the incubation period the 
cells were harvested onto GF/F glass fibre filters for later counting in a 
scintillation counter. Samples for chlorophyll, particulate organic carbon, 
pigment composition by HPLC, and absorption spectra were collected for each 
incubation experiment. 


Table A.4.2.3: P-I experiments conducted during the HUD2014007 mission in the 
               Labrador Sea. 

Station  Event    Lat.     Long        Date         Time      Depth    ID 
-------  -----  -------  --------  -------------  ----------  -----  ------
L3-17      33   57.7957  -51.3347  "May 07 2014"  "14:57:26"    1.7  400146 
L3-17      33   57.7957  -51.3347  "May 07 2014"  "14:55:46"   29.0  400137 
L3-20      47   59.0698  -49.9388  "May 08 2014"  "14:09:43"    1.1  400242 
L3-20      47   59.0698  -49.9388  "May 08 2014"  "14:07:57"   29.5  400233 
L3-27.5    67   60.5077  -48.2927  "May 09 2014"  "14:56:20"    1.9  400363 
L3-27.5    67   60.5077  -48.2927  "May 09 2014"  "14:53:25"   30.4  400353 
L3-22      86   59.7465  -49.1602  "May 10 2014"  "13:42:37"    2.2  400465 
L3-22      86   59.7465  -49.1602  "May 10 2014"  "13:40:42"   30.3  400456 
L3-16.5    96   57.5865  -51.5723  "May 11 2014"  "13:07:56"    3.0  400561 
L3-16.5    96   57.5865  -51.5723  "May 11 2014"  "13:04:09"   31.2  400552 
L3-05     120   54.487   -54.7505  "May 13 2014"  "14:44:07"    2.9  400802 
L3-05     120   54.487   -54.7505  "May 13 2014"  "14:41:18"   29.7  400793 
L3-9.5    137   55.3428  -53.9015  "May 14 2014"  "17:38:21"    2.3  400887 
L3-9.5    137   55.3428  -53.9015  "May 14 2014"  "17:36:06"   29.7  400878 




4. Major Problems and Goals Not Achieved 

   Not all AR07W sites could be occupied due to ice cover and weather. 



5. Other Incidents of Note 
 
   There were none to report. 



6. List of Cruise Participants (please update from Form B) 

Name                  Responsibility                  Affiliation 
--------------------  ------------------------------  -----------
Anning, Jeffrey       Biological                      OESD, BIO 
Clement, Pierre       Salts                           OESD, BIO 
Courchesne, Isabelle  VITALS, Winch Room Sampling     ULAV 
Duerkson, Steve       pH, O18                         DAL 
Duffy, Steve          Bird Observer                   EC 
Fung, Raymond         Technical Operations            PCSD, BIO 
Gagnon, Jonathan      VITALS, Winch Room Sampling     ULAV 
Geshelin, Yuri        Oxygens                         OESD, BIO 
Head, Erica           Biological Lead                 OESD, BIO 
Hsieh, Pei-Yuan       Winch Room Sampling             UCAL 
Jackson, Jeffrey      Data management, Computer Room  PCSD, BIO 
Jørgensbye, Helle     Biological, DNA                 Denmark 
LaBrie, Richard       VITALS, Winch Room Sampling     UM 
Laliberté, Julien     VITALS, Winch Room Sampling     UQAR 
King, Randy           Technical Operations Head, MVP  PCSD, BIO 
Nelson, Richard       Carbonate, Alkalinity           OESD, BIO 
Perry, Timothy        Biological, Net Tows            OESD, BIO 
Punshon, Stephen      Chemistry Lead, CFC-12, SF6     OESD, BIO 
Raimondi, Lorenza     Carbonate, Alkalinity           DAL 
Ringuette, Marc       Biological, Net Tows            OESD, BIO 
Ryan, Robert          CTD Tech., Winch Room, Floats   PCSD, BIO 
Sauve, Daniel         Chemistry                       UO 
Thamer, Peter         Nutrients                       OESD, BIO 
Wang, Zeliang         Computer Room                   DAL 
Wood, Dan             Electronics Tech, Winch Room    PCSD, BIO 
Yashayaev, Igor       Chief Scientist                 OESD, BIO 



BIO   Bedford Institute of Oceanography Dartmouth, Nova Scotia, Canada 

DAL   Dalhousie University 
      Halifax, Nova Scotia, Canada 

EC    Environment Canada 

OESD  Ocean Ecosystem Science Division 

PCSD  Program Coordination and Support Division 

UCAL  University of California 
      Berkeley, California, United States 

UM    University of Montreal 
      Montreal, Quebec, Canada 

UO    University of Ottawa 
      Ottawa, Ontario, Canada, K1N 6N5 

UQAR  University of Quebec at Rimouski 
      Rimouski, Quebec, Canada 

UVAL  University of Laval 
      Québec City, Québec, Canada 




B. UNDERWAY MEASUREMENTS 


1. Navigation and Bathymetry 

The differential GPS navigation system was provided onboard by the CCGS HUDSON. 
Navigation information was broadcast on the ships network for access in all lab 
areas. 

Mooring locations, station locations and navigation were monitored using the 
Aldebaran II electronic charting software from CNS Systems. 

All navigation data was logged using the Geological Survey of Canada’s (GSC) 
Survey Suite navigational software. A time and date stamp is added to each 
navigation string acquired. 

The echo sounder system included a Raytheon PTR echo sounder, a Raytheon Line 
Scan Recorder and an Edo 12kHz transducer. The Edo 12 kHz transducer was 
mounted on the ram located in the well on the forward deck and remained flush 
with the hull during the mission. 

A Benthos 7000 transducer was also mounted on the ram for use during mooring 
operations and mooring position and depth calibration. 


2. CTD Motion Study 

An attitude and heading reference sensor (Xsens MTi) was mounted on the CTD 
package. Data from the motion sensor was monitored in real-time to provide 
information on the dynamics of the package during a CTD cast. The Motion Data 
acquisition software combined each motion sensor sample with CTD and 
Instrumented Block System data. This information will hopefully aid in the 
prevention of motion induced failures in the mechanical wire termination on the 
CTD package. Motion data was logged at 10Hz for almost all CTD casts during 
this mission. 


3. Continuous Flow Multisensor Package (CFMP) 

Water from approximately 4m was continuously pumped to the forward lab. The 
temperature, conductivity and fluorescence were measured and logged every 15 
sec. The temperature and conductivity were measured with Sea-Bird 
Thermosalinograpgh and the fluorescence by a Wetlabs flow through fluorometer. 
Incident Photosynthetically Active Radiation was measured with a Li-Cor 
Spherical Quantum Sensor and this data was collected as hourly means. Exact 
time and positions were provided by the ships GPS and logged with the other 
data. Unfortunately the thermosalinograph system became unstable during the 
cruise so very little reliable data was collected. 


4. Meteorological observations 

The officer of the watch manually logged meteorological variables at regular 
intervals. 


5. Atmospheric Chemistry 

There was no atmospheric chemistry program. 




C. HYDROGRAPHIC MEASUREMENTS - DESCRIPTIONS, TECHNIQUES AND CALIBRATIONS 


1. Salinity 
   Pierre Clement 

Salinity samples were taken from rosette bottles and collected in hard glass 
bottles for analysis. The bottles were rinsed three times, the tops wiped dry 
and closed with new Polyseal caps tightened snugly. Samples were stored in 
trays and analysed using an Autosal 8400 salinometer. The system was set to run 
at 24°C. 

The instrument was setup Drawing Room of the Hudson. The pump was turned on and 
the system run for ~20-30 minutes to condition the instrument in advance of 
analysis. 


Calibration 

The Autosal was calibrated before and after analysis runs using OSIL standard 
seawater (SSW). The SSW bottle was immersed in a 22°C water bath to the neck to 
temperature condition, then shaken and blotted dry before opening. The analysis 
cell was emptied, the ‘sipping’ straw wiped dry and two rinses done before 
attempting to read the conductivity. Two separate reads were done and if the 
measures were consistent to 0.000001, the system adjusted to read the standard 
value. A second standard was processed following the same procedure to confirm 
the setting. The reference number was recorded and for any give machine that 
number tends to be stable from day to day assuming the room temperature is 
relatively constant and bath temperature set the same. If there is a deviation 
in the Ref number the analyst should be cautious about continuing. 
Sample Processing 

Sample analysis consisted of keeping sample trays in the 22°C water bath and 
the sample bottles were shaken by inversion, three times, left to settle for at 
least 30 seconds. The Autosal sipping straw wiped dry and the sample introduced 
with two complete washes before attempting to read. The third fill was read 
followed by a refill and read done to confirm the measure. If the read was 
within 0.000001 the value accepted, if not a third and subsequent reads done 
until there was a set of acceptable measurements. 

Once the sample run was completed a new calibration standard was run, following 
the above mentioned protocol and, if reasonable, the measure recorded and any 
change assumed to be system drift. The analyst has to assess whether there has 
been sufficient change in the Ref number and general conditions to accept any 
change in the SSW read value. A drift is not uncommon but the system can be 
very stable over long periods of time. 

All information was recorded on Bedford Institute of Oceanography Salinity Log 
Sheets. All fields were filled in and the data transcribed to an Excel 2010 
spreadsheet. To aid in quality control sample times were recorded at intervals, 
with particular emphasis in the start and end of a run and any breaks in 
operation within the run. These data were added to the spreadsheet and gaps 
filled in assuming 1.25 - 2.5 minutes between samples to match the recorded 
intervals. 


OPERATIONAL STORY 

The sample analyses were problematic the first couple days. The Autosal seemed 
to be working well but on May 12th there was significant drift between the 
start and end SSW and the Ref number did not seem stable. A decision was made 
to cut short the morning run, investigate the system more carefully and start 
the backup in case it was needed. The water chamber in the backup salinometer 
was empty and while filling it was noticed that the main Autosal chamber was 
not completely filled. Another 3-5 liters was added and once the system 
returned to 24 C a set of replicates were run to test its operation. Replicates 
were reserved to compare the two systems on May 13th. 

The replicates were run in the AM after warming the system up by running 20 - 
30 minutes of mock samples. From the replicate analysis the system seemed 
stable, so after lunch on May 13th sample analysis of regular samples 
continued. The backup system was not tested and left idle for the time being. 


     Date          Run     ID Start/Finish             Number Samples 
                   Number                              (Inc Std) 
     ------------  ------  --------------------------  --------------
     May  6, 2014   1      400014-079                    20 
     May  7, 2014   2      400080-121                    45 
     May  8, 2014   3      400152-215                    70 
     May  9, 2014   4      400216-261                    23 
     May 10, 2014   5      400267-379                    77 
     May 10, 2014   6      400380-433                    45 
     May 11, 2014   7      400434-521                    66 
     May 12, 2014   8      400522-575                    34 
     May 13, 2014   9      400576-665                   104 
     May 14, 2014  10      400666-833                   102 
     May 15, 2014  11      400834-926                   101 
     May 17, 2014  12      400957-975                    16 
     May 20, 2014  13      400981-1095                   77 
     May 21, 2014  14      401096-191                    91 
     May 22, 2014  15      401197-1278 (with 50 reps)   165 
     May 23, 2014  16      401284-1405                  101 
     May 24, 2014  17      401411-1474                   31 
     Totals        17                                  1164 


Replicates 

As part of the regular sampling the Chief Scientist included the collection of 
replicate samples which were to be run as ‘aged samples’ to look at changes in 
conductivity over time in un-opened sample bottles. This concept was expanded 
to include several sets of replicates to also look at Autosal/analyst 
performance over time. There is a concern that there is a temporal effect both 
in sample quality the longer samples were in bottles and a systematic 
instrumentation drift through the period of an analytical run. 

After the problems on the 13th and the system stabilized, which resulted in the 
use of several OSIL standards, it was suggested that replicates might serve as 
a means to assess whether there had been drift in the run. 

These statistics will be discussed further. 


DATA PROCESSING 

Conductivity measurements were written on Bedford Institute of Oceanography 
Salinity Log Sheets and transcribed to an Excel 2010 workbook. The QAT files 
from CTD operations were also copied to the workbook allowing for analysis of 
differences between manual (AutoSal) and instrumental determinations. 

The AZOMP Matlab scripts (compute_run_sal.m and compute_sal.m) were used to 
calculate salinities from the measured conductivities and with respect the 
standardization values with drift corrections. 


Excel Workbook 
SalinityCompareMMMDD.xlsx 

1. QAT – all the QAT file data 

2. CTDSalts – Subset of the QAT files including, ID, Date, Time of bottle 
   closure at depth, Instrument Salinity for each of the two CTD conductivity 
   cells, Event number and rosette bottle number 

3. Salinity – transcription of the conductivity data from the Log Sheets. 
   Includes function to calculate salinity from conductivity and bath 
   temperature as well as date and time of Autosal analysis for each of the 
   runs. 

4. Uncorrected Salts – Subset of the Salinity worksheet with Run number, 
   date/time. ID and salinity. No drift corrections were applied. 

5. Delta Salts – A lookup version of each the manual salinities from Salinity 
   and CTD salinities from QAT and the difference between the Manual salinity -
   CTD 1 (Delta1) and Manual salinity -CTD 2 (Delta2). Includes time of autosal 
   analyses ID, Run number and Event number. 

6. 2014007Cond – Export from Salinity with fields for Jeff J Compute_sal.m 
   a. Crun = Run Number 
   b. ID = Identifier 
   c. Crep = Replicate number within the run 
   d. Ctime = DateTime of analysis 
   e. Cond = measured Conductivity 
   f. Bath_Temp = Temperature of Autosal bath 

7. 2014007StdSw- Export from Salinity 
   a. Srun = Run Number 
   b. Svalue = Standard Conductivity, set at start of run and read within or at 
      end of run 
   c. Stype = ???? 
   d. Stime = DateTime of analysis 

8. Replicates – subset of Delta Salts for all manual sample that were run as 
   replicates. Includes all the fields in Delta Salts. 


Matlab 

A few simple Matlab scripts (compute_run_sal.m, Salt_ana_AllEvents_test1.m, 
ReplicateStats.m) were written as part of the assessment of error in the manual 
Salinity processing. These scripts were written to: 

1. plot out the Delta (Autosal – CTD1 salinities) for each of the runs on a 
   scale of ±0.005 salinity units with a breakout by the Event number. The 
   images of generated from the plots for each run will be used to help 
   understand the source of error. 

2. Display all the Differences over time by Event 

3. Look at the replicate stats 


RESULTS 

Manual salinities are used primarily on the Labrador Sea missions to calibrate 
the Seabird Salinity Conductivity Temperature and Depth (CTD) instrumentation 
estimates. Historically the Seabird CTD has proved very reliable and stable 
after proper sensor calibration and the manual or Autosal measurements have 
only been used as a check (pers. Comm., Igor Yashayaev). The chief scientist 
has expressed concern that there seems to be some systematic error in the 
Autosal salinities (salts) and has asked that this be looked at. For the 
purposes of this work, the Autosal Salts will be considered with respect to the 
CTD estimates as the difference between Autosal-CTD in Salinity units. 

The Seabird CTD has two conductivity sensors in order to provide redundancy. 
When the differences between the sensors (Figures C.1.1 & C.1.2) were plotted 
it was evident that there was a problem with 9 of the CTD1 estimates. These 
values show up as a tail just under 35 PSU in a plot of the two sensors (Figure 
C.1.3). The slope and R2 of the linear fit suggest that there is a -0.0432 
offset between the two sensors. The chief scientist suggested he had more 
confidence in the Primary or CTD1 sensor, so for the purposes of investigating 
error in the sample salinities the CTD1 sensor will be considered, except for 
the 9 odd values where CTD2 will be used. 

A comparison of CTD1 and the drift corrected Autosal estimates (Figure C.1.4) 
using a regression analysis shows a large number of outliers, with an R2=0.89, 
n=1169, a slope of 0.94 and an intercept of 1.996. As a rough check, removing n 
= 95 outliers that are identified as differing by ±0.01 PSU the regression 
changes dramatically with the Autosal over estimating the CTD by 0.0327 (Figure 
C.1.5) with an R2 = 1, thus looks like a reasonable offset correction. 

A plot of the Autosal-CTD1 salinities broken out by run number shows no obvious 
trend by run (Figure C.1.6). There are a series of 7 points that seem to line 
up in a secondary line above the main line but they are not replicates or can 
the offset be explained. 

Finally a little experiment was run to look at whether salinity quality was 
affected by sampling order. Traditionally the ‘Mission sampling order’ takes 
precedence over any Research sampling done by groups that join the mission for 
their own purposes and are outside of the Mission mandate. In general the 
‘normal’ order includes priority to volatile substances like gasses (DO, 
Freons, etc.) whose concentrations may be altered as the sample bottle warms up 
in the winchroom after recovery. On HUD2014007 a group from Laval Uni. 
collected Nitrous Oxide (NO) and Methane (CH4) gaseous sub-samples, but being 
Research priority these samples were taken all Mission samples including 
Salinity and nutrients. Given concern for loss of volatiles by waiting and 
alternatively worry that the salinities could be contaminated, a little 
experiment was run where duplicate Salts were subsampled in normal position and 
a second set taken after the Research gasses were collected. This Before and 
After experiment is presented below. 


Manual Salinity Error 

The source of the error in estimating salinity manually is a product of three 
main factors. Error can be introduced at sampling, through storage and at the 
analytical stage. There can also be data entry errors but these are readily 
identified and have been corrected for this dataset. 

For this assessment the assumption is that the CTD1, and the 9 CTD2, estimates 
are accurate although they may be shifted through a calibration. The outliers 
of the difference between AutoSal and CTD1 are then products of one of the 
three sources of error. 


Sampling and Analytical Error 

Estimating the error attributable to mishandling of the samples at collection 
and analysis is difficult to separate and assess. The suggestion here is to 
look at trends in runs and over the whole set of runs to allow for comment on 
any analytical drift. The spread of the difference over time may also identify 
some analytical systematic error. To elucidate the contribution of sampling 
error it is suggested that the amount and spread of the differences by event 
should show whether there was some aspect in sample handling that could be 
attributed to the event and thus related to some practice at the time of sample 
collection. 

To assess any analytical error it would be expected that the ideal set of 
AutoSal - CTD1 (Delta) differences would straddle Delta = 0 noting that there 
is probably a positive offset, so in the best case the values should tend to be 
above the line. The chief scientist suggested that error should be evaluated 
with the ±0.005 bounds. 

Looking at Delta against date and time of analysis, there seems to be a trend 
in analytical error from runs 1 through 17 in a negative direction (Figures 
C.1.7 & C.1.8). The same trend is evident when looking at Delta against 
Identification number, which can serve as a surrogate for time but spreads the 
numbers out (Figure 9). Looking more carefully at each run the tendency is the 
same with 9 runs above (2,3,5,6,7,8,9,12,17), 3 neutral or bounding 0 
difference (4,10,11) and 5 below (1,13,14,15,16) (Figures C.1.9 – C.1.11). 
To look at the sample handling the AutoSal - CTD1 difference (Delta) was 
plotted for each analytical run and color coding the differences by Event 
number (Figures C.1.10 – C.1.12). The expectation is that if there was a 
sampling handling problem then there could be a broader spread in Delta or some 
other standout anomaly when looking at the data from the event point of view. 


Storage or Bottle Effect 

There is a general consensus that manual salinities need to be done relatively 
soon after collection and that the longer the sample remained in a hard glass 
bottle the sample would degrade. Also analysis at sea is considered an issue 
because of poor temperature control in the lab which can affect the operation 
of the instrument. A practice of conditioning the samples by putting the trays 
in a water bath prior to analysis has sped the procedure up and added more 
confidence to the analysis. There is a discussion that maybe the analyses 
should be done post mission, on shore, so assessing the bottle effect will help 
in that decision. 

To look at this bottle effect, several sample replicates were taken and run at 
different intervals after the original sampling. The date and time of analysis 
was recorded as well as when the rosette bottle was closed at depth collecting 
the sample. The difference between collection and analysis date was determined 
as ‘Days since Collection’ and plotted against the AutoSal - CTD1 or Delta 
(Figure C.1.13). 

There were only 17/356 Delta values greater than ±0.005 and these occur at 
various times between 0.05 and 8.9 days after collection. The plot shows that 
the error does not display a trend of analysis from time of collection, if 
anything the error looks stable. The mean Delta is 0.0131 (stdv = 0.17144, N = 
356) removing three outliers (-1.0 < Delta > 1.0) yields a mean of -0.00094 
(stdv = 0.06545, N = 353). 

The 356 replicate samples are plotted against the number of replicates taken 
for each sample (Figure C.1.14). The expectation is that the more replicates 
the lower the mean difference (Delta) and a reduced standard deviation. The 
plot shows that trend suggesting again that there is no bottle effect. The few 
outliers were duplicates or triplicates and ranged from 0.5 days to 8 days from 
when the samples were collected. 


Before and After Experiment 

This experiment was quickly proposed to look at whether sampling salinities was 
affected by sub-sampling before Research gases or after. Fourteen sets of 
duplicates were collected in the normal priority and a second set collected 
‘After’ the Research gases. 

All samples were analysed in the same Run with the Mission Salts analysed in 
the normal analytical run order while the After Salts in a group. 

One set of samples was rejected because there was only a singlet for the After 
or Research duplicate. The analysis of the 13 sets of duplicates was to look at 
the average Delta for each duplicate set and the Average and standard deviation 
of the groups. 

The data show that there is no significant difference between the Deltas using 
a T-Test (P0.05 = 0.384 or > 0.01). The means difference is actually lower for 
the After or Research sub-samples but not significantly so. 


Table C.1.1: Statistics from the Beginning and End Test. The values represent 
             the average difference between AutoSal - CTD1 for each set of 
             duplicates taken before (Mission) and after the Research Gases 
             (Research).

                        ID          Mission   Research 
                        ---------  --------  ----------
                        401199     -0.0028   -0.00199 
                        401207     -0.0029   -0.00015 
                        401213     -0.0030   -0.00104 
                        401216     -0.0011   -0.00203 
                        401229     -0.00065  -0.00184 
                        401232     -0.00131  -0.00092 
                        401237     -0.00134  -0.00124 
                        401241     -0.0012   -0.00173 
                        401245     -0.00593  -0.00574 
                        401259     -0.00128  -0.00099 
                        401263     -0.00191  -0.00102 
                        401267     -0.00169  -0.00129 
                        401274      0.008004  0.007315 
                        MeanDiff   -0.0013   -0.0010 
                        StdevDiff   0.003118  0.002824 


Figure C.1.1: Difference between the Primary and secondary Salinity estimates 
              plotted against Pressure. 

Figure C.1.2: Difference between Primary and Secondary Temperature sensors 
              plotted against Pressure. 

Figure C.1.3: Primary (CTD1) vs Secondary (CTD2) salinity estimates. Notice 
              offset just under 35PSU caused by some irregularity in CTD1 
              estimate; resulting in CTD2 being used in subsequent analyses. 

Figure C.1.4: Primary salinity estimate versus the Autosal estimate; includes 
              all outlier data. 

Figure C.1.5: CTD1 versus AutoSal estimates with outliers removed and anomalous 
              CTD1 estimates replaced by CTD2 estimates. 

Figure C.1.6: CTD1 versus Autosal broken out by Analytical Run. Note inset 
              showing the CTD1 anomalous data. These points were replaced using 
              CTD2 for the subsequent analysis of error. 

Figure C.1.7: Delta plotted against date and time analysed. 

Figure C.1.8: All Delta by Time of analysis, broken out by Event. 

Figure C.1.9: Delta against the sample Identifier. This can be interpreted as a 
              surrogate of time but is not very accurate. It does display the 
              trend from a minor positive to negative error over the course of 
              the mission. 

Figure C.1.10: Delta for each Run broken out by the Event when they were 
               collected (Runs 1 – 8). 

Figure C.1.11: Delta for each Run broken out by Event number (Runs 9-15). 

Figure C.1.12: Delta for each Run broken out by Event number (Runs 16-17). 

Figure C.1.13: Replicate Delta against day since sample was collected. Inset 
               shows that there are 5 values that are outliers ranging between 
               0.5 and 8 days since collection. 

Figure C.1.14: Replicate Mean and Standard Deviations ordered by the number of 
               replicate samples collected. Inset shows that 5 sets of 
               replicates were outside the ±0.01 window (Outliers and all out 
               of less than three replicates. 



2. Measuring Dissolved Oxygen Concentration and calibration of Sea-Bird oxygen 
   sensors on the HUDSON 2014-007 mission. 
   Yuri Geshelin 
   11-FEB-2015 


1. Introduction 

In May of 2014, the CCGS Hudson carried out the annual field mission of the 
Atlantic Zone Off-shelf Monitoring Program (AZOMP): cruise 2014-007, which 
included the spring occupations of the ARW7 (WOCE) transect across the Labrador 
Sea and of the Extended Halifax line across the Scotian Shelf, Slope and Rise. 
At various depths samples and standard measurements of dissolved oxygen (DO) 
were taken in accordance with the standard cruise program. This was 
accomplished with the use of titration methods and by means of Sea-Bird DO 
primary and secondary sensors. Preliminary attempts to calibrate both sensors 
were made during the cruise, taking into account the experience gained on 
previous cruises in 2010-2013. We employed the Winkler method of titration in 
our analysis. 

This note describes the methods of collecting samples, data acquisition and 
processing, and presents some preliminary results of the expedition in the form 
of quantitative estimates. The results are compared with those obtained on some 
previous cruises. 


2. Methods and procedures 

Oxygen sub-samples were drawn from 10-L bottles attached to the operational 24-
bottle Rosette Sampler. Air contamination of the samples was reduced to a 
minimum as much as possible. This was accomplished by drawing samples almost 
immediately after the Rosette Sampler was drawn on board. The only property 
that was in some cases sampled prior to DO was chlorofluorocarbon, as 
chlorofluorocarbon samples are more sensitive to atmospheric oxygen than DO. As 
usual, an attempt was made to draw at least one DO sample from every closed 
bottle. At CTD casts, when this was impossible due to operational constraints, 
some bottles (levels) were skipped. At some levels, more than one sample was 
drawn from the same Rosette bottle to ensure that the whole procedure is 
accurate. The analysis of these duplicates is presented in the current report. 

The oxygen sampling bottles were Iodine flasks with matched custom ground 
stoppers. The approximate volume of each flask is 125 mL. Precise volumes of 
flasks with the corresponding stoppers were determined gravimetrically prior to 
the cruise, and volume data were saved to titration programs. The flasks and 
matched stoppers are etched with identification numbers, and care is taken to 
ensure that flasks always correspond to their stoppers counterparts. 

A silicone tube was attached to the spigot of each Niskin sample bottle mounted 
on the CTD rosette. The other end of the tube was then attached to a flask, and 
each DO sample was drawn in succession through the tubing in accordance with 
the procedure described in L. Codispoti, 1988. First, the flask and stopper 
were thoroughly rinsed, and the tube was inserted in the flask all the way to 
its bottom. Next, the grip on the tube was slowly released to avoid introducing 
bubbles, and the flow was allowed to continue until at least three flask 
volumes were overflowed. The sampling tube was then rotated inside the flask 
and thus rubbed against the neck to prevent bubbles from forming on it. Next, 
the tube was slowly removed with continuous low flow to ensure that no air was 
trapped in the flask and the volume kept to the brim. Two reagents were then 
immediately added to oxidize the sample: 1.0 mL each Alkaline Iodide and 
Manganous Chloride. During this procedure, the tip of the spout was submerged 
under the surface of the sample. After that, the stopper was inserted carefully 
to avoid introducing air. The flask was then turned upside down several times 
but not vigorously shaken. This completed the collection of samples proper. 
Immediately upon the collection the samples were stored before the titration 
for at least 1 hour in a semi-dark place at room temperature. 

The employed method of titration was implemented with the use of a colorimeter 
and the “BOB” software developed by Caroline Lafleur at the Maurice Lamontagne 
Institute, Quebec. 



3. Analysis of duplicates 

As mentioned in the introduction, different numbers of duplicates were taken at 
different casts. These numbers are summarized in Table C.2.1. 


Table C.2.1: Number of duplicates (triplicates) taken at different casts. 

     Number of duplicates taken  Total number  Number of successful
       from a Rosette bottle     of instances      titrations 
     --------------------------  ------------  --------------------
                 2                    90              87 
                 3                    15              15 


We have analysed the differences between any two values of DO concentration 
derived by means of the Winkler method. More specifically, in our analysis, we 
took into account all possible combinations of paired values. For example, when 
three duplicates were taken, we computed the absolute values of the differences 
between the first and the second, the second and the third, the first and the 
third samples. In total, this approach allowed us to obtain 132 paired values, 
for which the titrations were successful. The histogram of absolute values of 
differences between these paired values is presented in Figure C.2.1. 

As seen from the figure, most of the differences fall in the 0 – 0.01 mL/L 
interval. This suggests that on average, the titrations were performed fairly 
accurately. By way of comparison, the similar histograms in percentage 
occurrence for the cruises in 2010 and 2011 are presented in Figure C.2.2. 
These field missions were carried out in the same area and same time of the 
year. We estimate 56% below 0.01 ml/L in 2014, compared to 58% and 41% in 2010 
and 2011. 



4. Problems 

There occurred only three freezes (lock-ups) of the computer designated for 
running BOB software. As in the past, they were dealt with by way of rebooting 
the PC, colorimeter and DOSIMAT. To prevent these freezes, when the colorimeter 
was left idle for a prolonged time (an hour or more), the same strategy was 
used as on the previous cruises (Geshelin, 2012). Namely, a faked titration of 
blank solution was started, and if it did not cause any freeze, it was 
immediately terminated. The comment “This was a test” was entered to instruct 
the processing software to discard such titration. 


Figure C.2.1: The histogram of differences (absolute values) between the DO 
              concentrations obtained from the same Rosette bottle by means of 
              the Winkler method. 

Figure C.2.2: The histogram of differences (absolute values, in percentage 
              occurrence) between the DO concentrations obtained from the same 
              Rosette bottle (Winkler method) on three cruises in 2010 – 2014 
              (Geshelin, 2011, and this report). 



5. Sea-Bird – Winkler comparisons 

As in the past, the ultimate goal of the intercomparisons between Sea-Bird and 
Winkler methods was to perform the calibration of the Sea-Bird sensors, as the 
chemical method is supposed to provide more accurate values. The comparisons 
were carried out for both primary and secondary sensors. The number of data 
points employed in the analysis is 1138 both for the primary and secondary 
sensors(4). 

Figure C.2.3 presents the results of comparisons in the form of Sea-Bird vs 
Winkler DO scatter plots for the raw (unedited) data. The left panels present 
the scatter plot of the two concentrations. Plotted on the right panels is the 
relationship between pressure and the difference between the two 
concentrations. As in the past, this measure was taken to check whether the 
differences are dependent on pressure. As expected, the unedited data contain 
many outliers, most of which are accounted for. For example, the obvious blue 
clusters in the lower and right parts of the panels are due to the malfunction 
of the titration equipment. Namely, during the titration, air bubbles were 
accidentally drawn into the silicon tubes, because the level of a reagent in a 
bottle became too low. This glitch and other similar situations were verified 
with the ship log, and the total of 59 outliers was removed. The Sea-Bird vs 
Winkler comparisons of the refined data set are presented in Figure C.2.4. As 
seen from the figure, the elimination of the outliers resulted in noticeably 
reduced scatter and higher SeaBird – Winkler correlation coefficients. For the 
primary sensor, the correlation coefficient increases from 0.96 to 1.00 and 
from 0.98 to 0.99 for secondary. 


(4) This includes the duplicates (see Section 3) and outliers. 


Figure C.2.3: Scatter plot of Sea-Bird vs Winkler DO concentrations (left 
              panels) and Sea-Bird – Winkler difference vs pressure (right 
              panels). (a) – primary; (b) - secondary Sea-Bird sensor. Outliers 
              were not removed. 


Closer inspection of Figure C.2.4b reveals that there is still a group of 
outliers (blue points in the middle of the panel). The absence of a similar 
group in Figure 4a suggests that this may be a problem with the secondary DO 
sensor. This issue is in need of further investigation. 

Based on the refined data set, the correlation coefficients between Sea-Bird – 
Winkler differences and pressure are –0.19 and –0.93 for the primary and 
secondary sensors respectively. This suggests that in the case of the secondary 
sensor the calibration process is significantly dependent on pressure. Such 
undesirable dependence took place on some earlier Hudson cruises (Geshelin, 
2011, 2012, 2014), but in the current data set the effect is most prominent 
(see Figure C.2.4b). It also suggests that the issue of the pressure term in 
the Sea-Bird calibration equation raised in the previous technical reports 
still needs to be addressed. It is seen from Figure C.2.4, that for both 
sensors the scatter is larger at shallower depths. 


Figure C.2.4: Scatter plot of Sea-Bird vs Winkler DO concentrations (left 
              panels) and Sea-Bird – Winkler difference vs pressure (right 
              panels). (a) – primary; (b) - secondary Sea-Bird sensor. Outliers 
              have been removed. 



6. Conclusions 

We have summarized the procedures for and results of sampling, measuring and 
calibrating the DO concentrations on the Hudson cruise in the spring of 2014. 
The two sets of results are presented: prior and after the elimination of 
outliers whose reasons are understood and accounted for. The reasons for the 
remaining outliers are yet to be investigated, but on the whole, they do not 
reduce the overall correlation. In fact, the highest level of our sampling and 
titration techniques was achieved on the cruise covered by this report. This is 
seen from Table C.2.2, which summarizes the Sea-Bird – Winkler correlation 
coefficients derived on 8 cruises. 


Table C.2.2: Correlation coefficients between Winkler- and Sea-Bird-derived 
             values of DO concentration. 

                                 Primary Sea-Bird  Secondary Sea-Bird 
       Cruise        Ship             sensor             sensor
      --------  ---------------  ----------------  ------------------
      2010-014      Hudson            0.46               N/A 
      2010-049      Hudson            0.97               0.87 
      2011-009      Hudson            0.93               0.94 
      2011-043      Hudson            0.99               0.99 
      2012-001  Martha L. Black       0.90               0.93 
      2012-042      Hudson            0.94               0.95 
      2013-008      Hudson            0.92               0.92 
      2014-007      Hudson            1.00               0.99
         


The main results are: 

• The issue of pressure-dependent Sea-Bird values still needs to be addressed 
  (see Section 5). 

• The histogram of differences between the DO concentrations obtained from the 
  same Rosette bottle by means of the Winkler method suggests that most 
  measurements were taken fairly accurate: 56% of all differences are below 
  0.01 ml/L. However, for the 2010 cruise (2010-049) this percentage was 
  higher: 58%. 

• The removal of outliers considerably reduces the scatter and improves the 
  correlation. However, some outliers are not yet accounted for. Most likely, 
  they are due to the problems with secondary DO sensor. 

• The database of all quality-controlled DO values obtained by Seabird and the 
  Winkler method in 2010-2014 has been created. It will be useful in the future 
  research. 



References 

1. Lou Codispoti, 1988. One Man's Advice on the Determination of Dissolved 
   Oxygen in Seawater. Technical note. 
2. Y.Geshelin, 2011. Measuring Dissolved Oxygen Concentration and calibration 
   of Sea-Bird oxygen sensors on the Hudson 2011-043 cruise. Technical report. 
3. Y.Geshelin, 2012. Measuring Dissolved Oxygen Concentration and calibration 
   of Sea-Bird oxygen sensors on the Hudson 2012-042 cruise. Technical report. 
4. Y.Geshelin, 2014. Measuring Dissolved Oxygen Concentration and calibration 
   of Sea-Bird oxygen sensors on the Hudson 2013-008 cruise. Technical report. 



3. Nutrients 
   Peter Thamer 


a. Description of Equipment and Technique 

Samples were analyzed for silicate, phosphate, nitrate (nitrate plus nitrite), 
nitrite and ammonia using a SEAL Autoanalyzer III. The analytical methods were 
the same used historically with the Technicon Autoanalyzer II: Technicon for 
Seawater Analysis (Silicate 186-72W, Phosphate 155-71W, Nitrate/Nitrite 158-
71W), .R. Kerouel and A. Aminot; ‘Fluorometric determination of ammonia in sea 
and estuarine waters by direct segmented flow analysis.’ Marine Chemistry 57 
(1997) 265-275. The phosphate method has been modified by separating the 
Ascorbic Acid (4.0 gm/l) from the Mixed Reagent. The modified Mixed Reagent 
instead of sample water was introduced at the start of the sample stream (0.23 
ml/min.) and the Ascorbic Acid was introduced separately between the two mixing 
coils (0.32 ml/min.) (Strain and Clement, 1996). 


b. Sampling Procedure and Data Processing Technique 

Duplicate nutrient samples were drawn into 30 ml HDPE (Nalgene) wide mouth 
sample bottles from the 10 L Rosette bottles. The sample bottles were pre-
washed in 10% HCL, rinsed three times with NANOPure ultra-pure water and oven 
dried at >100 Degrees F. 

A sample run included six duplicate Calibration Standards at the beginning plus 
duplicates of the second most concentrated Calibration Standard for drift 
followed by a blank for detection limit and a baseline check run every 8 sample 
duplicates. The standards, wash water and blanks for phosphate, silicate and 
nitrate/nitrite were made up in 33 ppt NaCl (Sigma, ACS Reagent); for ammonia 
and nitrite, NANOPure water only. The quality of analysis was checked by 
analyzing an Intercalibration Reference Material MOOS-3 for nutrients produced 
by NRC, Ottawa. There is no existing ammonia Reference Material. 

The data was collected and concentrations calculated by the SEAL AA-3 
analytical software program provided with the new instrument. The data was 
reported as collected and stored on the hard drive (backed up on memory stick). 


c. Shipboard Analysis 

Total number of duplicate samples analyzed for AR7W Labrador Sea Mission 
HUD2014-007: 1205 (including the Halifax Line). Any samples collected off watch 
were kept refrigerated (4ºC) and analyzed within twelve hours of collection. 
Samples collected at Halifax Line Station 2 through the year have always been 
frozen. To duplicate sample treatment, samples collected at that station were 
frozen and processed on the fourth day of shipboard analysis. This station was 
sampled a second time (our last station), and will be analyzed back at BIO. 

All 5 nutrients were analyzed at sea: nitrate/nitrite, silicate, phosphate, 
ammonia and nitrite. The Barnstead NANOPure system was brought on board along 
with 340 litres of lab produced NANOPure water in acid washed 20 litre carboys. 
This water was purified again with the Barnstead system just before making up 
all reagents, including the 33‰ NaCl wash water. 

The Autoanalyzer III was assembled in the Geo-Chem lab this year to minimize 
temperature fluctuations and for the added stability of being lower in the 
ship. Phosphate and ammonia levels began to rise in wash water if left exposed 
in the lab for too long. To minimize changes in detection limits due to the 
increasing phosphate and ammonia levels over time, wash water was changed every 
half hour. The heaters used in phosphate and ammonia analysis were off for 
samples 400308 to 400381 resulting in questionable data for phosphate and 
unfortunately no data for ammonia. Some issues occurred with phosphate the 
night of May 10th as random drift cups (second highest standard) throughout the 
run were showing values equal to or greater than the highest standard. Flushing 
the line with strong acid seemed to solve the problem. The auto analyzer pump 
required maintenance on the 15th of May as there were some issues with peak 
shape (SiO) and baseline drift (NO3) from the previous night. Despite a 
different peak shape the samples looked consistent throughout the run. When 
plotted by Igor, there were noticeable differences between the surrounding 
stations. 

An Intercalibration Reference Material MOOS-3 produced by NRC, Ottawa was used 
as a check for data quality (except for Ammonia). Unfortunately, the supply of 
MOOS-3 is now limited and therefore was not run daily. May 14th nitrate results 
were high, due to the gradual degradation of the cadmium column over the course 
of the run. Nitrate values also seem to be consistently a little high due to 
the drift correction (over correcting). 



                    NO3+NO2        NO2 
          QC\QA     NITRATE      NITRITE      PHOSPHATE    SILICATE 
          MOOS-2      μM           μM            μM          μM 
         --------  ----------  -----------  ------------  ----------
         Accepted  24.9+/-1.0  3.31+/-0.18  1.58 +/-0.10  28.8+/-1.0 
          Values   
         --------  ----------  -----------  ------------  ----------
         06-May-14    26.85       3.60          1.783       28.27 
                      26.94       3.70          1.760       28.47 
         07-May-14    26.71       3.40          1.769       28.69 
                      26.80       3.25          1.760       28.66 
         13-May-14    26.87       3.45          1.728       28.97 
                      26.74       3.40          1.708       28.72 
         14-May-14    26.64       3.50          1.580       29.85 
         Corrected    26.61       3.60          1.578       29.74 
         18-May-14    27.12       3.45          1.607       29.19 
                      27.23       3.40          1.625       28.98 
         19-May-14    26.89       3.45          1.619       28.70 
                      26.90       3.65          1.624       28.48 


         Det. Limits  NITRATE  NITRITE  PHOSPHATE  SILICATE  AMMONIA 
             <DL        μM       μM        μM         μM       μM 
         -----------  -------  -------  ---------  --------  -------
          06-May-14    0.18     0.04      0.012      0.10     0.525 
          07-May-14    0.43     0.06      0.055      0.07     0.103 
          08-May-14    0.40     0.02      0.025      0.35     0.096 
          09-May-14    1.26     0.04      0.119      0.12     0.375 
          10-May-14    0.67     0.01      0.014      0.08     0.173 
          11-May-14    0.90     0.03      0.076      0.08     0.325 
          12-May-14    0.63     0.08      0.120      0.05     0.173 
          13-May-14    0.18     0.03      0.045      0.14     0.338 
          14-May-14    0.68     0.05      0.058      0.08     0.345 
          15-May-14    0.05     0.04      0.020      0.06     0.326 
          16-May-14    0.23     0.03      0.028      0.08     0.209 
          18-May-14    0.16     0.03      0.009      0.11     0.220 
          19-May-14    0.06     0.04      0.015      0.26     0.248 
          20-May-14    0.19     0.03      0.169      0.77     0.200 
          21-May-14    0.06     0.04      0.018      0.04     0.167 
          22-May-14    0.07     0.03      0.006      0.18     0.101 
          23-May-14    0.11     0.03      0.012      0.37     0.240 




4. Ocean Chemistry Group 
   Stephen Punshon (June 20, 2014) 


Transient Tracers SF6 and CFC-12 

Seawater samples from the rosette were drawn directly into 250 mL glass 
syringes which were then stored at ~ 4 °C in a low-temperature incubator for up 
to 12 hours. Immediately before analysis, the samples were warmed to around 20 
°C in a water bath then injected into the purge vessel of a custom made purge-
and trap system where dissolved gases were stripped from the sample in a stream 
of ultra high purity nitrogen with a flow rate of 120 mL per minute. SF6 and 
CFC-12 were quantitatively retained in a trap comprising 30 cm of 1/16" 
stainless steel tubing packed with 100-120 mesh Carboxen 1000 held at -70 °C in 
a dewar containing liquid nitrogen. After each 7 minute purge cycle, the trap 
was heated to 180 °C with a low voltage electric current and the desorbed gases 
directed to a Varian gas chromatograph equipped with an electron-capture 
detector. SF6 and CFC-12 were separated on a 1 m pre-column packed with Porasil 
B and a 3 m main column packed with Molecular Sieve 5A held isothermally at 95 
°C. Total run-time was 11 minutes and 50 seconds for a water sample. The 
chromatographic sample peaks were quantified with Varian Galaxie software and 
the analytical system calibrated at least once each day using an air standard 
supplied by CMDL/NOAA, Boulder, Colorado. Analytical precision as determined by 
repeated standard injections was around ± 2 % for SF6 and ± 0.7 % for CFC-12. 

Eighteen seawater samples for SF6 and CFC-12 were typically collected from 
every deep CTD cast, this number being determined by the total stock of glass 
syringes (36 syringes in 6 racks) and available time between stations. On the 
Extended Halifax Line, the sampling density was increased to 24 depths at the 
deep stations. A total of 449 water samples were analysed for dissolved SF6 and 
CFC-12 on the AR7W line (Stations 3-28 plus extra intermediate stations) and 
315 on the Extended Halifax Line (Stations 2-19). Air samples were collected 
from the upwind side of the ship during the outward transit to the AR7W line to 
measure the atmospheric mole fractions of SF6 and CFC-12 in order to calculate 
seawater saturation states. Twenty six air samples were analysed, giving mean 
atmospheric mixing ratios of 8.44 ± 0.10 parts per trillion for SF6 and 527.6 ± 
10.9 parts per trillion for CFC-12. 


pH 

Samples for pH analysis were collected from every depth at Stations 3 – 28 on 
the AR7W line, and from every depth at stations 2-19 on the XHL. In addition, 
samples were collected from selected depths at shallow biological stations on 
the AR7W and Extended Halifax Lines where the SeaBird pH sensor was deployed. 
Seawater was analysed for pH according to the spectrophotometric method 
described in “Guide to best practises for ocean CO2 measurements” SOP 6B, 
edited by Andrew Dickson. Water was collected from the rosette in 60 mL 
borosilicate glass tubes, allowing each sample to overflow by at least one 
volume. Racks of tubes were then placed in a water bath held at 25 °C and 
allowed to thermally equilibrate for 30 minutes. Each sample was then 
introduced into a water-jacketed 10 cm quartz cell and 30 μL of the indicator 
dye m-cresol purple added before mixing well. The absorbance of light at the 
wavelengths 434 and 578 nm was measured with an Agilent photodiode array 
spectrophotometer and the resulting extinction coefficients at these 
wavelengths were used to determine the pH of the sample. Measurements were 
conducted during both night and day shifts and samples were stored in a low 
temperature incubator at 4 °C until immediately prior to analysis. The maximum 
time between sampling and analysis was about 4 hours. The sample absorption 
spectra were not referenced to a Certified Reference Material as in the past 
due to the current unavailability of these CRMs. A total of 623 pH samples were 
analysed from the AR7W line and 342 from the Extended Halifax Line. 


Total Inorganic Carbon (TIC) and Total Alkalinity (TA) 

A total of 780 seawater samples from whole number stations 3-28 on the AR7W and 
2-19 on the XHL were collected in 500 mL borosilicate glass bottles and 
preserved with mercuric chloride following the method described in “Guide to 
best practises for ocean CO2 measurements”. The samples were subsequently 
transported back to the Bedford Institute of Oceanography for analysis. TIC was 
later determined using gas extraction and coulometric titration with 
photometric endpoint detection (Johnson, et al., 1985). Total alkalinity was 
measured by open-cell potentiometric titration with full curve Gran Point 
determination using a Titrando dosimat with Tiamo software in conjunction with 
a sample delivery system built in-house. Bottles of Batch 134 Certified 
Reference Material (CRM) (supplied by Professor Andrew Dickson, Scripps 
Institution of Oceanography, San Diego, USA) were analyzed in duplicate at 
intervals to evaluate accuracy. 


Discrete pCO2 

Water samples for pCO2 measurements were drawn from the rosette (following 
dissolved oxygen) into 160 mL volume crimp seal vials, allowing each sample 
vial to overflow by about 2 volumes before immediately preserving with 50 μL of 
saturated mercuric chloride solution and crimp sealing with butyl rubber septa. 
The samples were stored at 4 ºC until the return to BIO. Surface samples were 
collected from every station throughout the cruise and full depth profiles were 
collected from Stations 17 and 18 on the AR7W line. pCO2 was later determined 
by headspace equilibrium gas chromatography. 


Underway pCO2 

A Pro-Oceanus pCO2 sensor was plumbed into the underway seawater de-bubbler and 
distribution manifold located above the sink in the forward lab. Data from this 
was acquired almost continuously throughout the cruise on a PC running 
Docklight RS232 terminal software. 


Sampling Stations 

Stations 3 to 28 were sampled on the AR7W line, stations 1 and 2 were 
inaccessible due to sea ice. Additional stations 19.5, 17.5, 14.5, 11.5 and 
10.5 were sampled for transient tracers in order to provide extra resolution in 
the upper 1800 m of the water column. On the Extended Halifax Line, whole 
number stations 2 to 19 were all sampled. 

Sample identification numbers ranged from 400001 to 400939 on the AR7W line and 
401015 to 401474 on the Extended Halifax Line. 


Additional sample collection 

Full profiles of samples for δ18-O were collected in 60 mL Boston Round bottles 
from every whole-number station on the AR7W line on behalf of Dalhousie 
University. Additionally, 5 profiles of samples for δ13-C TIC were collected 
from the AR7W Line in ~300 mL BOD bottles, also for Dalhousie University. 


Sampling and Analytical Problems 

The non-original spigot taps fitted to the Niskin bottles continue to present a 
contamination problem for transient tracer measurements, particularly in the 
deep abyssal water of the Extended Halifax Line, where concentrations of SF6 
are extremely low. A number of Niskin bottles persistently leaked during the 
first few days of sampling but this problem was eventually rectified. 

No analytical problems were encountered. 



5. VITALS Biology Team 
   PI’s: 
   Simon Bélanger (UQAR), 
   Roxane Maranger (Université de Montréal) 
   Jean-Éric Tremblay (Université Laval) 


   Cruise Participants: 
   Jonathan Gagnon & Isabelle Courchesne (Université Laval) 
   Julien Laliberté (UQAR) 
   Richard LaBrie (Université de Montréal) 


1. General objectives. 

The main objectives of the VITALS biology team were to: 

1) understand how physical properties and nutrient availability in different 
   water masses affect the structure of microbial communities and the rates of 
   new and regenerated primary production, bacterial production, respiration 
   and key nitrogen cycling steps along the AR7W line in the Labrador Sea, and 

2) obtain in situ optical measurements that will serve to refine remote-sensing 
   algorithms. 


2. Methods 


2.1. Water sampling, incubations and biogeochemical measurements 

The list of stations and variables measured is provided at the end of this 
document (Table 1). 

• In addition to the core nutrient samples taken by BIO, samples for inorganic 
  nutrients were taken in the bottles from which we took water for our 
  incubations (Biology cast). Samples for nitrite, nitrate, orthophosphate, 
  silicate and urea were frozen for subsequent analysis at Laval University 
  using a Seal Analytical AutoAnalyzer 3. Ammonium and urea samples were 
  processed immediately after collection using the fluorometric method of 
  Holmes et al. (1999) and the colorimetric method of Goeyens et al. (1998), 
  respectively. 

• Deck incubations with trace additions of 15N-labeled nitrogen sources 
  (nitrate, ammonium, urea) were performed to estimate daily rates of nitrogen 
  assimilation, nitrification and microbial ammonification at 6 different 
  depths (0, 10, 20, 30, 40, and 60 m). Incubations were terminated by 
  filtration onto GF/F filters. Filters were dried and stored for subsequent 
  analysis of the amount and isotopic enrichment of particulate organic N by 
  Isotope-Ratio-Mass-Spectrometry at Laval University. Filtrates were killed 
  and stored refrigerated. The dissolved ammonium contained in filtrates will 
  be extracted by the diffusion technique of Raimbault and Garcia (2008) to 
  obtain microbial ammonification rates. Nitrification rates will be obtained 
  by converting nitrate to N2O using the bacterial denitrification method (e.g. 
  Christman et al. 2011). 

• Parallel incubations with 14C-bicarbonate were made to estimate daily net 
  primary production. We assessed the amounts of 14C retained in the 
  particulate organic pool (POC), passing into dissolved organic carbon pool 
  (DOC) and accreted in the particulate inorganic pool (PIC, providing an 
  estimate of calcification) (Gosselin et al. 1997, Paasche and Brubak 1994). 
  Bacterial production was estimated from short-term 3H-leucine incorporation 
  and bacterial respiration was assessed by Winkler titration after 3 hours of 
  incubation. 

• Water from the upper mixed layer was pump continuously using the ship’s water 
  intake and analyzed for core properties (nutrients, temperature, chlorophyll) 
  by BIO collaborators and net community production (NCP) by us using the O2/Ar 
  method with equilibrator inlet mass spectrometry (EIMS) (Cassar et al. 2009). 
  This measurement integrates biological processes over the time scale of a 
  week. The data will also be used to provide spatial context for the discrete 
  sampling and to ground truth satelitte-based estimates of PP. Discrete 
  determinations of O2/Ar will be used to post-calibrate the EIMS (Hamme, gases 
  team). 

• Additional samples were taken at the surface and in the subsurface 
  chlorophyll maximum (or 30 m) to determine pigments (HPLC), the elemental C, 
  N, P, Si composition of particulate organic matter, the concentration of 
  cocolithophores and the taxonomic composition of the phytoplankton community. 
  Samples were also taken for the determination of bacterial abundance by 
  epifluorescence microscopy (DAPI staining) and flow cytometry. DNA was 
  preserved on 3-μm and 0,8-μm filters for subsequent molecular analysis of 
  bacterial diversity. 


2.2. Optical deployments 

The list of deployment sites is provided at the end of this document (Table 2). 

• The C-OPS (Biospherical Instruments) was deployed from the foredeck with 
  partial success due to problems of pitch and roll during the instrument’s 
  free fall. This sensor measures apparent optical properties (spectral 
  downwelling irradiance and upwelling radiance at 19 wavelengths across the 
  ultraviolet-visible-near infrared domains). Another sensor package measuring 
  inherent optical properties (spectral absorption and backscattering 
  coefficients) along with fluorescent dissolved organic matter, temperature 
  and salinity was successfully deployed. 



References 

Cassar et al. 2009. Continuous high-frequency dissolved O2/Ar measurements by 
    Equilibrator Inlet Mass Spectrometry (EIMS). Analytical Chemistry. 81:1855-
    1864. 

Christman et al. (2011) Abundance, Diversity, and Activity of Ammonia-Oxidizing 
    Prokaryotes in the Coastal Arctic Ocean in Summer and Winter. Appl. 
    Environ. Microbiol. 77 :2026-2034. 

Goeyens et al. 1998 Estuarine, Coastal and Shelf Science (1998) 47, 415–418 

Gosselin et al. (1997) New measurement of phytoplankton and ice algal 
    production in the arctic ocean. 

Holmes et al. (1999) Can J Fish Aquat Sci 56:1801–1808 

Paasche and Brubak (1994) Enhanced calcification in the cocolithophorid 
    Emiliania Huxleyi (Haptophyceae) under phosphorus limitation. Phycologia 
    33: 3324-330. 

Raimbault P, Garcia N. (2008). Evidence for efficient regenerated production 
    and dinitrogen fixation in nitrogen-deficient waters of the South Pacific 
    Ocean: impact on new and export production estimates. Biogeosciences 5: 
    323–338 



Table 1:  List of sampling stations and measurements made on water obtained 
          from the Biology Rosette cast


                                             Nitrogen  Primary     
Date        Station    Frozen  Fresh  Fresh  uptake &  produc-   15N/18O  
                        nuts    NH4   Urea   POC/PON    tion    of nitrate
----------  ---------  ------  -----  -----  --------  -------  ----------
05/05/2014  NFL-SHELF    X       X      X       X         X         X     
05/07/2014  L3_17        X       X      X       X         X         X     
05/08/2014  L3_20        X       X      X       X         X         X     
05/09/2014  L3_27,5      X       X      X       X         X         X     
05/10/2014  L3_22        X       X      X       X         X         X     
05/11/2014  L3_16,5      X       X      X       X         X         X     
05/13/2014  L3_05        X       X      X       X         X         X     
05/14/2014  L3_9,5       X       X      X       X         X         X     
05/15/2014  NFL_SHELF1   X       X      X       X         X         X     
05/16/2014  NFL_SHELF2   X       X      X       X         X         X     
05/20/2014  HI-17        X       X      X       X         X         X     
05/21/2014  HL-14        X       X      X       X         X         X     
05/21/2014  HL-13        X       X      X       X         X         X     
05/22/2014  HL-10        X       X      X       X         X         X     
05/22/2014  HL-9,5       X       X      X       X         X         X     



Date        Station    Pigments  POP  BioSi  Cocolito- Taxonomy  CDOM  
                         HPLC                 phores                   
----------  ---------  --------  ---  -----  ---------- --------  ----  
05/05/2014  NFL-SHELF      X      X     X       X         X        X   
05/07/2014  L3_17          X      X     X       X         X        X   
05/08/2014  L3_20          X      X     X       X         X        X   
05/09/2014  L3_27,5        X      X     X       X         X        X   
05/10/2014  L3_22          X      X     X       X         X        X   
05/11/2014  L3_16,5        X      X     X       X         X        X   
05/13/2014  L3_05          X      X     X       X         X        X   
05/14/2014  L3_9,5         X      X     X       X         X        X   
05/15/2014  NFL_SHELF1     X      X     X       X         X        X   
05/16/2014  NFL_SHELF2     X      X     X       X         X        X   
05/20/2014  HI-17          X      X     X       X         X
05/21/2014  HL-14          X      X     X       X         X
05/21/2014  HL-13          X      X     X       X         X
05/22/2014  HL-10          X      X     X       X         X
05/22/2014  HL-9,5         X      X     X       X         X



Date        Station    DOC/TDN  Bacterial    Bacterial   Bacterial  DNA  O-N-Ar
                        /TDAA   production  respiration  abundance       gases
----------  ---------  -------  ----------  -----------  ---------  ---  ------
05/05/2014  NFL-SHELF     X         X            X          X        X     X
05/07/2014  L3_17         X         X            X          X        X     X
05/08/2014  L3_20         X         X            X          X        X
05/09/2014  L3_27,5       X         X            X          X        X
05/10/2014  L3_22         X         X            X          X        X
05/11/2014  L3_16,5       X         X            X          X        X
05/13/2014  L3_05         X         X            X          X        X
05/14/2014  L3_9,5        X         X            X          X        X
05/15/2014  NFL_SHELF1    X         X            X          X        X     X
05/16/2014  NFL_SHELF2    X         X            X          X        X
05/20/2014  HI-17      
05/21/2014  HL-14      
05/21/2014  HL-13      
05/22/2014  HL-10      
05/22/2014  HL-9,5     



Table 2: List of deployments for apparent optical properties

Stations      Repeat casts  UTC Time
------------  ------------  --------
Test-Station        1       14:22:29
                    2       14:25:09
L3_20               1       14:48:37
                    2       14:51:25
                    3       14:55:49
                    4       14:58:35
                    5       15:00:51
L3_27,5             1       15:32:17
                    2       15:34:30
                    3       15:36:18
L3_22               1       14:02:56
                    2       14:05:13
                    3       14:07:18
                    4       14:11:12
                    5       14:11:32
                    6       14:12:07
                    7       14:13:35
                    8       14:14:24
L3_9,5              1       18:15:57
                    2       18:18:18
                    3       18:21:26
                    4       18:23:25
NFL_SHELF1          1       15:56:12
                    2       15:58:57
                    3       16:01:02
                    4       16:04:08
                    5       16:10:19
HL-17               1       17:25:06
                    2       17:28:44
                    3       17:31:11
                    4       17:33:07
                    5       17:34:28
                    6       17:37:38



CCHDO Data Processing Notes

Date        Person        Data Type    Action     Summary
----------  ------------  -----------  ---------  -----------------------------
2014-10-08  Diggs, Steve  CTD/BTL/DOC  Submitted  WOCE formatted data
            One ZIP archive includes WOCE formats for CTD and BOT.  Two cruise 
            reports included.  ExpoCode needs to be changed from 33KB258/1 to 
            33KB20131219.

