Ea h Sys . Sci. Da a, 12, 2747–2763, 2020
h ps://doi.o g/10.5194/essd-12-2747-2020
© Au ho (s) 2020. This wo k is dis ibu ed unde
he C ea i e Commons A ibu ion 4.0 License.
Physical and biogeochemical pa ame e s
o he Medi e anean Sea du ing a c uise wi h
RV Ma ia S. Me ian in Ma ch 2018
Dagma Hainbuche 1, Ma a Ál a ez4, Blanca As ay Uceda4, Gianca lo Bachi5, Vanessa Ca din3,
Paolo Celen ano6, Spy os Chaikalis7, Ma ia del Ma Cha es Mon e o3,9, Giuseppe Ci i a ese3,
Noelia M. Faja 4, F ancois F ipia 10, Lenna Ge ke2, Alexand a Gogou7, Elisa F. Gualla 4,
Bi e Gülk1, Abed El Rahman Hassoun8, Nico Lange2, And ea Rochne 1, Chia a San inelli5,
Tobias S einho 2, Tos e Tanhua2, Lidia U bini3, Dimi ios Velao as7, Fabian Wol 2, and
And eas Welsch1
1Ins i u ü Mee eskunde, CEN, Uni e si ä Hambu g, Bundess aße 53, 20146 Hambu g, Ge many
2GEOMAR, Helmhol z-Zen um ü Ozean o schung Kiel, Wischho s . 1–3, 24148 Kiel, Ge many
3Dep . O Oceanog aphy, Is i u o Nazionale di Oceanog a ia e di Geo isica Spe imen ale – OGS,
Bo go G o a Gigan e 42/c, 34010 Sgonico, T ies e, I aly
4Ins i u o Español de Oceanog a ía (IEO), Cen o de A Co uña, Spain
5Is i u o di Bio isica, CNR, Pisa, I aly
6Is i u o di Scienze Ma ine, Venezia, I aly
7Hellenic Cen e o Ma ine Resea ch, A hens, G eece
8Na ional Council o Scien i ic Resea ch in Lebanon, Na ional Cen e o Ma ine Sciences, Bei u , Lebanon
9Cen o Eu o-Medi e aneo sui Cambiamen i Clima ici CMCC, Bologna, I aly
10Max Planck Ins i u e o Chemis y, Mainz, Ge many
Co espondence: Dagma Hainbuche (dagma .hainbuche @uni-hambu g.de)
Recei ed: 2 Ap il 2020 – Discussion s a ed: 7 July 2020
Re ised: 17 Sep embe 2020 – Accep ed: 29 Sep embe 2020 – Published: 12 No embe 2020
Abs ac . The las ew decades ha e seen d ama ic changes in he hyd og aphy and biogeochemis y o he
Medi e anean Sea. The complex ba hyme y and highly a iable spa ial and empo al scales o a mosphe ic
o cing, con ec i e and en ila ion p ocesses con ibu e o gene a e complex and uns eady ci cula ion pa e ns
and signi ican a iabili y in biogeochemical sys ems. Pa o he a iabili y o his sys em can be in luenced
by an h opogenic con ibu ions. Consequen ly, i is necessa y o documen de ails and o unde s and ends
in place o be e ela e he obse ed p ocesses and o possibly p edic he consequences o hese changes. In
his con ex we epo da a om an oceanog aphic c uise in he Medi e anean Sea on he Ge man esea ch
essel Ma ia S. Me ian (MSM72) in Ma ch 2018. The main objec i e o he c uise was o con ibu e o
he unde s anding o long- e m changes and ends in physical and biogeochemical pa ame e s, such as he
an h opogenic ca bon up ake and o u he assess he hyd og aphical si ua ion a e he majo clima ological
shi s in he eas e n and wes e n pa o he basin, known as he Eas e n and Wes e n Medi e anean T an-
sien s. Du ing he c uise, mul idisciplina y measu emen s we e conduc ed on a p edominan ly zonal sec ion
h oughou he Medi e anean Sea, con ibu ing o he Med-SHIP and GO-SHIP long- e m epea c uise sec ion
ha is conduc ed a egula in e als in he Medi e anean Sea o obse e changes and impac s on physi-
cal and biogeochemical a iables. The da a can be accessed a h ps://doi.o g/10.1594/PANGAEA.905902
(Hainbuche e al., 2019), h ps://doi.o g/10.1594/PANGAEA.913512 (Hainbuche , 2020a)
h ps://doi.o g/10.1594/PANGAEA.913608, (Hainbuche , 2020b) h ps://doi.o g/10.1594/PANGAEA.913505,
(Hainbuche , 2020c) h ps://doi.o g/10.1594/PANGAEA.905887 (Tanhua e al., 2019) and
h ps://doi.o g/10.25921/z7en-hn85 (Tanhua e al, 2020).
Published by Cope nicus Publica ions.
2748 D. Hainbuche e al.: Physical and biogeochemical pa ame e s o he Medi e anean Sea in Ma ch 2018
Da a co e age and pa ame e measu ed
Reposi o y Re e ence. Table 1a and b and lis o a ailable
da a se s (Table 1c).
A link o he summa y page o he c uise MSM72 can
be ound in he PANGAEA da abase unde h ps://www.
pangaea.de/?q=msm72& .campaign%5B%5D=MSM72
(las access: 10 No embe 2020).
Co e age. 34–41◦N, 6◦W–28◦E
Loca ion name. The Medi e anean Sea
Da e/Time s a . 2 Ma ch 2018
Da e/Time end. 3 Ap il 2018
1 In oduc ion
Con a y o ea lie ideas ha he Medi e anean Sea is always
in a s eady s a e, we now know in he ligh o new esea ch
ha he Medi e anean Sea is no , and i is po en ially sensi-
i e o clima ic changes (Malano e-Rizzoli, 2014). P o ing
his a e he d as ic changes ha he eas e n Medi e anean
(EMed) has unde gone in he pas . The la ges clima ic e en ,
named he Eas e n Medi e anean T ansien (EMT), occu ed
in he EMed be ween he la e 1980s and ea ly 1990s, whe e
deep-wa e o ma ion swi ched om he Ad ia ic Sea o he
Aegean Sea. This episode modi ied he he mohaline cha -
ac e is ics o he ou low h ough he Sicilian S ai , ad ec -
ing anomalously sal y and wa m Le an ine In e media e Wa-
e (LIW) o he wes e n Medi e anean Sea (WMed) and
leading o a signi ican inc ease in empe a u e and sal in
he in e media e and deep laye s o he WMed. Addi ion-
ally, s ong deep con ec ion induced by ex eme a mosphe ic
e en s du ing win e in 2004–2006 (low p ecipi a ion, cold,
pe sis en winds) also enhanced sal and empe a u e in he
en i e basin up o abou 1600m (Sch oede e al., 2006,
2008). This ab up clima e shi is e e ed o as Wes e n
Medi e anean T ansien (WMT) and he physical changes
a e compa able o he EMT, bo h in e ms o in ensi y and
obse ed e ec s (Sch oede e al., 2008). The exis ence o
bo h ansien s con adic s he hypo hesis o a s eady s a e.
On he o he hand, i has also been p o en ha an EMT has
ne e been obse ed be o e (Roe he e al., 2013).
The cha ac e is ic o he Medi e anean Sea is also such
ha i has he po en ial o seques e la ge amoun s o an h o-
pogenic CO2, Can , since he Medi e anean Sea has high al-
kalini y and empe a u e, which can be apidly anspo ed
o deep by he o e u ning ci cula ion (e.g., Schneide e
al., 2010). The column in en o ies o Can in he Medi e -
anean a e among he highes ound in he wo ld oceans;
he Medi e anean Sea hus s o es a signi ican po ion o he
global an h opogenic emissions o Can despi e i s ela i ely
small olume.
Fu he mo e, ma ine dissol ed o ganic ca bon (DOC)
ep esen s he la ges ese oi o educed ca bon (662×
1015 g C) on Ea h (Hansell, 2009), i he e o e plays a ma-
jo ole in he global ca bon cycle. I s ole in he unc ion-
ing o ma ine ecosys ems is equally c ucial since DOC is
eleased a all he le els o he ood web as a byp oduc
o many ophic in e ac ions and/o me abolic p ocesses and
is he main sou ce o ene gy o he he e o ophic p oka y-
o es (Ca lson and Hansell, 2015). Al hough mos o DOC is
p oduced in si u, ex e nal sou ces (a mosphe e, i e s, sedi-
men s) may a ec i s concen a ion and dis ibu ion. Physical
p ocesses, such as deep-wa e o ma ion, he mohaline ci -
cula ion, e ical s a i ica ion and mesoscale ac i i ies ha e
been epo ed o be he main d i e s o DOC dis ibu ion
in he Medi e anean Sea (San inelli, 2015; San inelli e al.,
2015, 2013).
The main scien i ic objec i e o he c uise epo ed he e
was o add knowledge o he di e en scales and magni udes
o a iabili y and ends in ci cula ion, hyd og aphy, and bio-
geochemis y o he Medi e anean Sea. Key a iables we e
measu ed in s a egic egions in o de o unde s and changes,
he eason o occu ence, and he d i e s. In his con ex , his
c uise is pa o he Med-SHIP and GO-SHIP long- e m e-
pea c uise sec ion ha is conduc ed a egula in e als in
he Medi e anean Sea o obse e changes and impac s on
physical and biogeochemical a iables.
The ollowing science ques ions a e add essed in his
wo k.
1. Wha a e he long- e m changes and/o ends in physics
and biochemis y in he Medi e anean Sea, including
all he sub-basins?
2. How is he hyd og aphic si ua ion in he Medi e anean
de eloping u he ollowing he EMT and WMT? Is
he e s ill a endency o he sys em o e u n o he p e-
EMT si ua ion and is he e a simila end in he WMed?
3. How a e eddies dis ibu ed in he EMed and WMed du -
ing he c uise? Do hey di e in he sub-basins? To wha
ex en is hea and sal ans e ed in o he e ical by ed-
dies in he WMed and EMed du ing he c uise pe iod?
4. Wha is he up ake a e o he an h opogenic ca bon in
he Medi e anean and is his changing o e ime?
5. Wha is he ex en o he a iabili y and ends in he in-
en o y o biogeochemical a iables (including oxygen,
nu ien s and dissol ed o ganic ca bon)?
6. Wha a e he baseline alues o a ely measu ed essen-
ial ocean a iables (EOVs) such as dissol ed o ganic
ca bon (DOC)?
Ea h Sys . Sci. Da a, 12, 2747–2763, 2020 h ps://doi.o g/10.5194/essd-12-2747-2020
D. Hainbuche e al.: Physical and biogeochemical pa ame e s o he Medi e anean Sea in Ma ch 2018 2749
Table 1. (a) Lis o physical pa ame e s om Ma ia S. Me ian c uise MSM72 as seen in he PANGAEA da abase. The p ima y in es iga o
was Dagma Hainbuche . (b) Lis o biogeochemical pa ame e s om Ma ia S. Me ian c uise MSM72 as seen in he CCHDO da abase. The
p ima y in es iga o was Tos e Tanhua. (c) Lis o a ailable da a se s.
(a)
Pa ame e name Sho name Uni Me hod Commen s
Da e/ ime Da e/ ime Geocode
La i ude La i ude Geocode
Longi ude Longi ude Geocode
P essu e, wa e P ess dba CTD, SEA_BIRD SBE 911plus
Tempe a u e, wa e Temp ◦C CTD, SEA_BIRD SBE 911plus
Salini y Sal CTD, SEA_BIRD SBE 911plus
Oxygen O2µmolkg−1CTD wi h a ached oxygen senso (SBE43) cal-
ib a ed, co ec ed using Winkle i a ion
P essu e, wa e P ess dba Unde way CTD (uCTD), Oceanscience
Tempe a u e, wa e Temp ◦C Unde way CTD (uCTD), Oceanscience
Salini y Sal Unde way CTD (uCTD), Oceanscience
Dep h, wa e Dep h m
Cu en eloci y eas –wes UC ms−1Shipboa d acous ic dopple cu en p o iling
(SADCP)
Cu en eloci y no h–sou h VC ms−1Shipboa d acous ic dopple cu en p o iling
(SADCP)
Dep h, wa e Dep h m
Cu en eloci y eas –wes UC ms−1Lowe ed acous ic dopple cu en p o iling
(lADCP)
Cu en eloci y no h–sou h VC ms−1Lowe ed acous ic dopple cu en p o iling
(lADCP)
(b)
Va iable Uni
Dissol ed oxygen (O2) µmolkg−1
Sul u hexa luo id (SF6) molkg−1
CCl2F2(CFC-12) pmolkg−1
Ni a e (NO−
3) µmolkg−1
Ni i e (NO−
2) µmolkg−1
Phospha e (PO2−
4) µmolkg−1
Silica e (Si) µmolkg−1
Dissol ed ino ganic ca bon (DIC) µmolkg−1
To al alkalini y (TA) µmolkg−1
pH To al scale a 25 ◦C
Ca bona e (CO2−
3) µmolkg−1
δ13C o DIC ‰
To al dissol ed ni ogen (TDN) µmolkg−1
To al dissol e phospho us (TDP) µmolkg−1
CHClF2(HCFC-22) pmolkg−1
C2H3Cl2F (HCFC-141b) pmolkg−1
C2H3ClF2(HCFC-142b) pmolkg−1
CH2FCF3(HFC-134a) pmolkg−1
C2HF5(HFC-125) pmolkg−1
CHF3(HFC-23) pmolkg−1
h ps://doi.o g/10.5194/essd-12-2747-2020 Ea h Sys . Sci. Da a, 12, 2747–2763, 2020
2750 D. Hainbuche e al.: Physical and biogeochemical pa ame e s o he Medi e anean Sea in Ma ch 2018
Table 1. Con inued.
(c)
Da abase Da a se
h ps://doi.o g/10.1594/PANGAEA.905902 CTD (Hainbuche e al., 2019)
h ps://doi.o g/10.1594/PANGAEA.913512 uCTD (Hainbuche , 2020a)
h ps://doi.o g/10.1594/PANGAEA.913608 ADCP (Hainbuche , 2020b)
h ps://doi.o g/10.1594/PANGAEA.913505 lADCP (Hainbuche , 2020c)
h ps://doi.o g/10.1594/PANGAEA.905887 chemical da a (Tanhua e al., 2019)
h ps://doi.o g/10.25921/z7en-hn85 pCO2(Tanhua e al., 2020)
h ps://cchdo.ucsd.edu/c uise/06M220180 (addi ional) CTD and chemical da a
2 Da a p o enance
The su ey was ca ied ou on he Ge man RV Ma ia S.
Me ian om 2 Ma ch o 3 Ap il 2018. The c uise s a ed
on He aklion, G eece, and ended in Cádiz, Spain. The main
ocus o he c uise was on an eas –wes ansec ac oss he
wes e n and eas e n Medi e anean Sea (Fig. 1) s a ing eas
o C e e and ending nea he S ai o Gib al a , which is a
epea ing hyd og aphic line in GO-SHIP (MED1). Di icul-
ies wi h diploma ic au ho iza ions o Ma ine Scien i ic Re-
sea ch (MSR) in he a ea eas o C e e made i impossible
o us o ca y ou ou measu emen s as ini ially planned, and
hus no da a we e ob ained eas o he Kasos S ai .
Du ing he 33 d o he c uise we ca ied ou measu emen s
o hyd og aphic and biogeochemical a iables along ack
wi h he classical app oach, i.e., CTD, lADCP, uCTD in-
s umen a ion and bo le samples on highly esol ed sec ions
ac oss he Medi e anean Sea. The high esolu ion o CTD
s a ions, enhanced o he physical pa ame e s by addi ional
uCTD measu emen s, allowed us o esol e he eddy ield
on he sec ions; he analysis was also suppo ed and comple-
men ed by sa elli e da a.
Mos sec ions and CTD-posi ions ollow p e ious sam-
pling s a egies (c uise M84 and o he s along he GO-SHIP
line MED-01, i.e., Tanhua e al., 2013) o allow long- e m
end analyses. Along he di e en sec ions, CTD s a ions
including sampling o chemical pa ame e s we e conduc ed
app oxima ely e e y 30nm, CTD wi hou sampling abou e -
e y 15–20 nm and wi h e en smalle spacing in he s ai s. In
addi ion, unde way CTD measu emen s and ADCP measu e-
men s we e pe o med be ween CTD s a ions.
The wa e sampling p og am included measu emen s o
all le el 1 a iables as de ined by GO-SHIP (i.e., oxy-
gen, mac onu ien s, ansien ace s and he ca bona e
sys em, h p://www.go-ship.o g/Da Req.h ml, las access:
10 No embe 2020) and measu emen s o he biogeochem-
ical EOVs 13C, ni ous oxide (N2O) and dissol ed o ganic
ca bon (DOC). These da a we e used o quan i y ends and
a iabili y o en ila ion and biogeochemical cycles, in pa -
icula up ake o an h opogenic ca bon.
Sec ions we e addi ionally conduc ed h ough he impo -
an passages o he O an o S ai , Kasos S ai , An iky he a
S ai , Sicilian S ai and S ai o Gib al a , in o de o cha -
ac e ize he incoming and ou going lows. CTD s a ions in
he eas e n Ionian Sea we e ca ied ou o quan i y he low
o he Le an ine Su ace Wa e (LSW) in o he Ad ia ic Sea
and o ack he ou low o he Ad ia ic Deep Wa e (AdDW)
in o he Ionian Sea.
3 Me hods
3.1 CTD ose e
All oge he 136 CTD cas s we e pe o med, om which
18 we e ca alogued as iso opic (a ull sui e o obse a ions
is gi en in Table 1a and b), 65 as chemical (i.e., GO-SHIP
le el 1 a iables) and 59 as physical (i.e., only sampling o
salini y). Due o he wa e amoun needed, wo cas s we e
pe o med on mos o he iso opic s a ions, he i s cas was
a ull p o ile and he second a shallow one. Du ing he phys-
ical s a ions, wa e samples a h ee le els we e aken o
salini y analysis. The samples we e hen analyzed on boa d
using a Guildline Au osal Salinome e . A o al o 162 sam-
ples in 59 s a ions we e aken du ing he c uise wi h an o se
wi h espec o s anda d wa e a ying om 0.0002 o 0.0030
depending on he labo a o y empe a u e. The samples we e
aken a dep h wi h a cons an salini y g adien o ensu e ha
no na u al changes in salini y a ec he compa ison be ween
sample and senso .
The p ima y CTD sys em ( o speci ica ions, see Table 2)
ini ially used on boa d was a Seabi d SBE9plus+CTD s/n
0285 om he Uni e si y o Hambu g connec ed o a SBE11
deck uni , con igu ed wi h a 24-posi ion SBE-32 pylon ( om
GEOMAR) wi h 10 L Niskin bo les. The posi ion o bo le
no. 23 and no. 24 was occupied by he lADCP ( o spec-
i ica ions, see Table 3). Ini ially, he CTD was se up wi h
wo senso s o empe a u e and conduc i i y, an oxygen sen-
so , a luo ome e , and an al ime e . To es he con igu a ion
and pe o mance o he ins umen a s a ion was ca ied ou
on he C e an Sea a he s a o he c uise. Un o una ely,
we had coun less p oblems wi h ins umen s, senso s, cables
Ea h Sys . Sci. Da a, 12, 2747–2763, 2020 h ps://doi.o g/10.5194/essd-12-2747-2020
D. Hainbuche e al.: Physical and biogeochemical pa ame e s o he Medi e anean Sea in Ma ch 2018 2751
Figu e 1. S a ion map. Yellow do s a e CTD wi hou any chemical sampling, ed do s a e CTD wi h chemical sampling, cyan do s a e
CTD wi h chemical and addi ional sampling o iso opes, yellow squa es a e he deploymen o d i e and loa s, blue lines a e ine esol ed
uCTD and ADCP acks, and black lines a e acks wi h uCTD cas s be ween CTD s a ions. (a) De ail o he cen al map o he wes e n
Medi e anean Sea. (b) De ail o he cen al map o he eas e n Medi e anean Sea. (c) De ail o he cen al map o he O an o S ai and
no he n Ionian Sea. (d) De ail o he cen al map o he Ty henian Sea and Sicilian S ai .
and he ose e du ing mos o he campaign ha o ced us
o change hem e y o en wi h o he s a ailable on boa d, e-
sul ing in a con inuous change o sys em con igu a ion. Thus,
all di e en con igu a ions we e ca e ully conside ed when
pos -p ocessing he CTD da a.
Tempe a u e, salini y and p essu e da a we e pos -
p ocessed by applying Seabi d so wa e and MATLAB® ou-
ines. A his s age, spikes we e emo ed and 1dba a e ages
calcula ed. A i s a emp o assess he pe o mance o he
conduc i i y senso s ins alled on he CTD ose e was done
by compa ing he salini y da a wi h he bo le samples ana-
lyzed wi h he salinome e . The di e en ha dwa e se ups and
con igu a ions a e aken ca e ully in o accoun du ing pos -
p ocessing. O e all accu acies a e wi hin he expec ed ange
o salini y (0.003).
3.2 Unde way CTD
Unde way CTD measu emen s (uCTD; o speci ica ions,
see Table 4) p o ide high- esolu ion p o iles o empe a u e,
conduc i i y and dep h, which allow us o cha ac e ize he
uppe -ocean p ope ies and iden i y he posi ion and cha ac-
e is ics o mesoscale s uc u es. The ad an age o his ype
o measu emen is ha i is no equi ed o s op he essel,
h ps://doi.o g/10.5194/essd-12-2747-2020 Ea h Sys . Sci. Da a, 12, 2747–2763, 2020

2752 D. Hainbuche e al.: Physical and biogeochemical pa ame e s o he Medi e anean Sea in Ma ch 2018
Table 2. Used CTD ins umen and senso s. Owne o ins umen s
a e ei he he Uni e si y o Hambu g, Ge many (I M-HH); he Na-
ional Ins i u e o Oceanog aphy and Geophysics (OGS), I aly; o
he p ope y o he essel Me ian (MSM).
Ins umen /senso Se ial numbe Calib a ion
(owne ) da e
SBE 911plus/917plus CTD 285 (I M-HH) 3 Dec 2014
806 (MSM) 27 Jan 2016
807 (MSM) 8 Sep 2015
Tempe a u e 1: SBE-3-02/F 1717 (OGS) 22 No 2017
5716 (MSM) 15 Jul 2017
Conduc i i y 1: SBE-4-02/2 3442 (OGS) 22 No 2017
4152 (MSM) 14 Jul 2017
Tempe a u e 2: SBE-3-02/F 1294 (I M-HH) 11 Ap 2017
5719 (MSM) 15 Jul 2017
Conduc i i y 2: SBE-4-02/2 1106 (I M-HH) 12 Ap 2017
4156 (MSM) 14 Jul 2017
Oxygen 1: SBE 43 3392 (OGS) 19 Dec 2017
2417 (MSM) 16 Aug 2017
0951 (MSM) 1 Dec 2017
Oxygen 2: SBE 43 1761 (I M-HH) 11 Ap 2017
2418 (MSM) 15 Aug 2017
0881 (MSM) 23 Dec 2017
Fluo ome e WETLAB 1755 (MSM) 18 Ap 2017
1754 (MSM) 21 Dec 2017
SeaPoin (used on 1 s a ion) SCF2874 unknown
SPAR 10 Ma 2016
PAR Chelsea 17 Oc 2016
i is only necessa y o main ain lowe eloci ies (abou 3kn)
du ing he deploymen s o each g ea e dep hs. These mea-
su emen s we e made wi h an Ocean Science uCTD sys em.
The i s uCTD deploymen was done on 5 Ma ch, be-
ween CTD 015 and 016 s a ions, and we con inued wi h
his ype o sampling be ween each CTD s a ion o inc ease
he sampling esolu ion. Un o una ely, se e al deploymen s
we e canceled due o se e e wea he condi ions and no uCTD
cas was pe o med when he dep h was shallowe han
500 m. All oge he , 176 cas s we e aken wi h dep hs ang-
ing om 557 o 864 m.
Two p obes we e used du ing he c uise wi h a no- ime-
limi mode con igu a ion (apa om he i s cas con igu ed
o s op eco ding a e 600 s, eaching 616 m dep h) in o de
o ge longe eco ds. The p obe ail spools we e a ached o
he winch h ough a ope loop ha was made new e e y day
in he mo ning. Despi e he p obes being able o eco d se -
e al cas s, da a we e downloaded igh a e each cas using
a SBE so wa e in o de o a oid losing he da a in case he
p obe was los and o ee up he memo y. The p obes we e
exchanged when he ba e y was unning low (a ound 3.8 V).
On h ee occasions no da a we e eco ded because he mag-
ne was aken o wice be o e deploymen .
Fo calib a ion pu poses, some addi ional cas s we e done
igh a e he CTD cas in o de o compa e he da a se s.
The p obes we e also sen down wi h he s a boa d CTD in
s a ion 130.
Da a iles we e p ocessed using a se o MATLAB® ou-
ines. A e ex ac ing he downcas da a, he i s co ec ion
was done o emo e inaccu acies in he descen a e, based
on he wo k o Ullmann and Hebe (2014). Addi ionally, he
da a we e aligned o he compa able CTD da a se s.
3.3 lADCP measu emen s
Ocean cu en s we e s udied by means o e ical p o iles
made wi h a lADCP-2 sys em (Wo kho se RD Ins umen s
ype, Table 3) which included wo ADCPs ope a ing a a e-
quency o 300kHz, one looking upwa d and he o he one
looking downwa d. The sys em was placed in he ose e oc-
cupying he posi ion o Niskin bo les 23 and 24. Du ing he
c uise, he lADCP ba e ies we e changed wice: he i s ime
on 17 Ma ch in S a ion 58 and he second ime on 27 Ma ch
in S a ion 105. Excep o h ee s a ions (s a ion 73, 74, 80)
wi h wa e dep hs less han 500m, lADCP measu emen s
we e done a all CTDs. Fo hese s a ions, he cu en s we e
obse ed by he ship-moun ed ADCP. A iso ope s a ions,
lADCP p o iles we e only eco ded om he deep cas . The
gained da a we e p ocessed wi h LDEO MATLAB®lADCP
p ocessing sys em e sion 10.15 (Tu nhe , 2014). This so -
wa e uses he aw lADCP da a, p ocessed CTD da a and na -
iga ional da a om he CTD. The esul ing da a a e he u- and
- eloci ies a he dep h. The bin size was se o 8 m.
3.4 Shipbo ne ADCP
Du ing he whole campaign, unde way cu en measu e-
men s we e aken wi h wo essel-moun ed Ocean Su -
eyo s (ADCP) manu ac u ed by RDI. The i s , wi h a
wo king equency o 75 kHz, co e ed app oxima ely he
op 500–700 m o he wa e column. The numbe o bins
was se o 100 wi h bin size o 8m. The second, wi h a
wo king equency o 38 kHz, has a dep h ange o abou
1600 m, se wi h he same bin numbe as he p e ious one
and bin size o 16 m. Bo h ins umen s un in na owband
mode and we e con olled by compu e s using he con en-
ional RDI VMDAS so wa e unde a Mic oso Windows
sys em wi h a pinging se o as as possible. No in e -
e ences wi h o he used acous ical ins umen s we e ob-
se ed. The ADCP da a was pos -p ocessed a e wa ds wi h
he CODAS3 So wa e Sys em (h ps://cu en s.soes .hawaii.
edu/docs/adcp_doc/, las access: 10 No embe 2020), which
allows ex ac ing da a, assigning coo dina es, and edi ing and
co ec ing eloci y da a. Mo eo e , he da a we e co ec ed
o e o s in he alue o sound eloci y in wa e , and mis-
alignmen o he ins umen wi h espec o he axis o he
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D. Hainbuche e al.: Physical and biogeochemical pa ame e s o he Medi e anean Sea in Ma ch 2018 2753
Table 3. Used uCTD senso s.
P obe 1 De ice ype Se ial numbe (owne )
0289 90745 uCTD/SBE49 Fas Ca CTD 702-0289 (I M-HH)
0183 90745 uCTD/SBE 49 Fas Ca CTD 702-0183 (I M-HH)
Table 4. Used lADCP.
De ice Type Se ial numbe (owne )
WHM300 Mas e s/n no. 22762 (I M-HH)
WHM300 Sla e s/n no. 22763 (I M-HH)
ship (abou −2.8◦ o 75 kHz ADCP and abou −0.15◦ o
38 kHz ADCP).
3.5 Unde way CO2and O2measu emen s
Unde way (UW) measu emen s o pa ial p essu e o CO2
(pCO2), and dissol ed oxygen pa ial p essu e (pCO2 he
co esponding da a se in Table 1b only con ains pCO2) in
seawa e we e ca ied ou by means o a Con os Hyd oC
pCO2analyze o pCO2and an Aande aa op ode o oxy-
gen.
The ins umen s we e placed in a cooling box in he
hanga . Seawa e was d awn om he ship’s cen i ugal
pump o clean seawa e ha was con inuously lowing
h ough he cooling box wi h he inle close o he ins u-
men s. Wa e was pumped h ough a SeaBi d 5 salini y and
empe a u e senso and on o he Hyd oC ins umen (Ge ke,
2020).
The sys em ope a ed eliably h oughou he c uise, excep
when da a acquisi ion was in e up ed o he pCO2ins u-
men o 2 d di ec ly a e he ship’s cen i ugal pump was
swi ched o . This led o a 5 d pe iod wi hou da a be ween
5 and 10 Ma ch. Du ing he c uise, 13 samples we e aken
om he cooling box o disc e e measu emen s o pH and
o al alkalini y. The UW measu emen s s a ed on 2 Ma ch a
20:20 and s opped on 1 Ap il 2018, a 14:00 UTC.
The unde way oxygen measu emen s we e calib a ed by
compa ing hem o he Winkle measu emen s aken o su -
ace samples a he chemical CTD s a ions.
3.6 Dissol ed oxygen
Dissol ed oxygen in seawa e was no only measu ed wi h
he CTD, bu samples we e also aken a e e y s a ion and
dep h along he c uise and epo ed in µmolkg−1. GO-SHIP
guidelines ecommend Winkle measu emen s on all sam-
ples, in addi ion o senso measu emen s on he CTD pack-
age, and we la gely ollowed hose ecommenda ions. Un-
o una ely, we had o ma k la ge numbe s o oxygen al-
ues de e mined wi h he CTD as ques ionable due o he se -
e al echnical p oblems wi h he CTDs and senso s. Usually,
samples we e aken a s anda d dep hs, bu , especially a he
su ace and a he bo om, he dep hs we e a ied acco d-
ing o he equi emen s o he o he biogeochemical pa ame-
e s. Oxygen was measu ed ollowing he au oma ic Winkle
po en iome ic me hod, modi ied ollowing Langdon (2010).
Ti a ions we e done wi hin he sampling calib a ed lasks
using an Au oma ic Ti a o Me le Toledo T50 wi h a pla -
inum combined elec ode.
Reagen s o blank and hiosul a e s anda diza ion
we e done daily by means o po assium ioda e s an-
da d 1.667 mmol by OSIL, UK. Abou 1400 samples we e
analyzed on boa d. The p ecision o dissol ed oxygen
measu emen s was de e mined on i e eplica es a he
beginning and a he end o he c uise (Table 5).
In addi ion, du ing he c uise 46 duplica es we e analyzed.
The esul s a e gi en in Table 6.
3.7 Nu ien s (ni i e, ni a e, phospha e and silica e),
o al dissol ed ni ogen (TDN) and o al dissol ed
phospho us (TDP)
3.7.1 Nu ien s
Analyses we e pe o med a 40 ◦C on a ou -channel,
Quaa o SEAL Analy ical Con inuous Flow Analyze
s/n 8014549; h ps://www.seal-analy ical.com/P oduc s/
Segmen edFlowAnalyze s/QuAA o39Au oAnalyze / abid/
814/language/en-US/De aul .aspx (las access: 10 No em-
be 2020), acco ding o Hansen and Ko ole (1999).
Ni i e was de e mined h ough he o ma ion o a eddish-
pu ple azo dye and measu ed a 520nm (SEAL Me hod
no. Q-030-04 Re . 2). Ni a e was educed o ni i e in a
coppe ized cadmium educ ion coil and hen de e mined as
desc ibed o ni i e (SEAL Me hod no. Q-035-04 Re . 4).
The de e mina ion o phospha e was based on he educed
blue phospho-molybdenum complex and hen measu ed a
880 nm (SEAL Me hod no. Q-031-04 Re . 1). Silica e was
de e mined by means o acidic educ ion o silicomolybda e
o molybdenum blue and hen measu ed a 820nm (SEAL
Me hod no. Q-038-04 Re . 0).
Abou 1400 nu ien samples we e analyzed on boa d. The
onboa d p ecision o nu ien measu emen s was de e mined
on i e eplica es a he beginning and a he end o he c uise.
The esul s a e shown in Table 7.
In addi ion, du ing he c uise 140 duplica es we e ana-
lyzed. The esul s a e shown in Table 8.
h ps://doi.o g/10.5194/essd-12-2747-2020 Ea h Sys . Sci. Da a, 12, 2747–2763, 2020
2754 D. Hainbuche e al.: Physical and biogeochemical pa ame e s o he Medi e anean Sea in Ma ch 2018
Table 5. P ecision o dissol ed oxygen (SD is s anda d de ia ion, and CV is coe icien o a ia ion).
Pa ame e Beginning o he c uise End o he c uise
Mean µM SD µM CV% Mean µM STD µM CV%
Dissol ed oxygen 196.07 0.13 0.07 198.84 0.14 0.07
Table 6. Resul s o duplica es.
Pa ame e Range Mean absolu e Mean Rela i e
(µM) di e encea(µM) pe cen age di e enceb
Dissol ed oxygen 179–240 0.18 0.09
aAD = | duplica e no. 1 −duplica e no. 2|.bRPD % =absolu e di e ence ·100 /mean (dupl. no. 1,
no. 2).
An in e nal quali y check was daily pe o med by means
o analyses o QUASIMEME samples, which p o ided e-
sul s wi hin he al eady ce i ied anges.
3.7.2 TDN and TDP
Abou 550 samples o o al dissol ed ni ogen and o al dis-
sol ed phospho us (TDN and TDP) on land-based labo a o y
analyses we e collec ed and ozen a −20 ◦C a e il a ion
on p e-combus ed GF/F il e . The dissol ed o ganic compo-
nen s, dissol ed o ganic ni ogen (DON) and dissol ed o -
ganic phospho us (DOP) we e subsequen ly calcula ed by
sub ac ing hei mine al cons i uen s (NO3+NO2) and PO4,
espec i ely.
3.8 Disc e e CO2sys em measu emen s
Disc e e CO2 a iables we e measu ed on boa d, i.e., dis-
sol ed ino ganic ca bon (DIC), pH, o al alkalini y (TA) and
ca bona e ion (CO2−
3); hese a iables we e measu ed a se-
lec ed s a ions and dep hs (Table 9). In addi ion, disc e e
samples o DIC, pH and TA we e analyzed speci ically om
su ace Niskin bo les o be compa ed wi h he con inuous
wa e supply eeding he pCO2sys em in de e mined s a-
ions. Fo u he de ails, especially abou he on-boa d p o-
cedu e o he measu emen o samples, see Hainbuche e
al. (2018).
3.8.1 DIC
Samples o DIC we e collec ed ollowing ansien ace s
and dissol ed oxygen in 500mL bo osilica e bo les ollow-
ing s anda d p ocedu e. No poison was added. Samples we e
le a oom empe a u e in he da k un il analysis a maximum
o 48 h a e collec ion. DIC samples we e analyzed wi h a
MARIANDA VINDTA 3D sys em coupled wi h a UIC 5011
coulome e . This analysis o e all consis s o ex ac ing sea-
wa e CO2 om a known olume o sample by adding phos-
pho ic acid, ollowed by coulome ic de ec ion (Johnson e
al., 1993). No calib a ion uni was a ailable o he sys em.
A new coulome ic cell was p epa ed o e e y ba ch o anal-
ysis and he accu acy o he DIC measu emen s was assessed
by using Ce i ied Re e ence Ma e ial (CRM no. 158 and
no. 170, p o ided by And ew G. Dickson, UCSD). The cali-
b a ion ac o ob ained om he CRM was used o adjus ing
he inal DIC o each sample measu ed in he co esponding
ba ch o analysis. In addi ion, subs anda d seawa e (s abi-
lized seawa e om he C e an Sea 700 m salini y minimum,
s o ed in he da k in a 30L con aine ) was analyzed a he be-
ginning and end o he ba ch analysis as a seconda y quali y
con ol. The p ecision o he DIC measu emen s was checked
by (1) double analysis om he same sample and (2) eplica e
analysis om ou o i e samples collec ed om he same
Niskin bo le. The p ecision is es ima ed o be 1 µmolkg−1,
and he accu acy is assumed o be 2µmolkg−1.
3.8.2 pH
Seawa e spec opho ome ic pH was measu ed ollowing
Clay on and By ne (1993) a almos all dep hs in he chemi-
cal and iso ope s a ions du ing he MSM72 c uise (Table 1).
This me hod consis s on adding a olume o indica o solu-
ion o he seawa e sample, so ha measu ing he abso bance
o he sample a di e en wa eleng hs and ob aining he a-
io be ween wo o he wa eleng h’s abso bance is p opo -
ional o he sample pH. The indica o was a 2mM solu-
ion o unpu i ied m-c esol pu ple (Sigma Ald ich®) p e-
pa ed in seawa e and main ained in he da k wi h no ai
con ac (abso bance a io o 1.30). Samples we e aken ol-
lowing s anda d p ocedu es immedia ely a e DIC and di-
ec ly in o cylind ical 10cm pa h leng h op ical glass cells.
The cells we e he mos a ized a 25±0.2◦C o 1 h be-
o e analysis. Abso bance measu emen s we e ob ained in
he he mos a ed chambe o a double-beam UV 2600 Shi-
madzu spec opho ome e . The equipmen was checked be-
o e he c uise o he abso bance and wa eleng h accu acy
using holmium s anda ds. The pH alues on he o al scale
Ea h Sys . Sci. Da a, 12, 2747–2763, 2020 h ps://doi.o g/10.5194/essd-12-2747-2020
D. Hainbuche e al.: Physical and biogeochemical pa ame e s o he Medi e anean Sea in Ma ch 2018 2755
Table 7. On-boa d p ecision o nu ien measu emen s.
Pa ame e Beginning o he c uise End o he c uise
Mean µM STD µM CV% Mean µM STD µM CV %
Ni i e (1) 0.01 0.01 100 0.03 0.01 56.5
Ni i e +ni a e 4.94 0.01 0.2 9.01 0.02 0.2
Phospha e 0.18 0.01 5.5 0.41 0.01 3.1
Silica e 8.34 0.03 0.3 9.55 0.04 0.5
Table 8. Analysis o duplica es.
Pa ame e Range Mean absolu e Mean ela i e
(µM) Di e encea(µM) pe cen age di e enceb
Ni i ec0–0.19 0.01 48.77
Ni i e +ni a e 0.33–9.86 0.02 0.42
Phospha e 0–0.47 0.01 5.13
Silica e 0.93–11.00 0.04 0.72
aAD = | duplica e no. 1 −duplica e no. 2|;bRPD % =absolu e di e ence ·100 /mean (dupl. no. 1,
no. 2). cNi i e s a is ics was gi en jus o comple eness, since he concen a ion le els eco ded we e
oo low and o en below he de ec ion limi .
Table 9. To al numbe o CO2sys em samples analyzed du ing he
MSM72 c uise. The o al numbe o i ed bo les was 1723.
DIC pH TA CO2−
3Su ace
Samples 479 1160 949 391 22
we e calcula ed and e e ed a 25◦C by using he o mula
by Clay on and By ne (1993). The injec ion o he indica-
o in he sample sligh ly changes he sample pH. Follow-
ing s anda d ope a ing p ocedu es, double addi ions o he
indica o we e pe o med o e a pH g adien in o de o ob-
ain he co esponding co ec ion (Hainbuche e al., 2018).
The pH accu acy was con olled measu ing TRIS bu e solu-
ion samples (ba ch no. 72, p o ided by And ew G. Dickson,
UCSD). TRIS samples we e s abilized a h ee di e en em-
pe a u es co e ing he pH ange ound du ing he MSM72
c uise. Di e ences be ween measu ed and heo e ical TRIS
pH a ied be ween 0.009 o 0.005. The pH p ecision was
checked by eplica e analysis om cells collec ed a he same
Niskin om su ace and deep wa e s. The p ecision is es-
ima ed o be 0.0004 pH uni s, and he accu acy was es i-
ma ed o be 0.005 pH uni s. Du ing he c uise, some samples
we e also analyzed wi h pu i ied m-c esol pu ple p o ided
by Robe H. By ne (USC).
3.8.3 TA
TA was analyzed ollowing a double end poin po en iome -
ic echnique by Pé ez and F aga (1987) u he imp o ed
by Pé ez e al. (2000). This echnique is as e han he
whole cu e i a ion, wi h compa able esul s (Min op e
al., 2000). TA was measu ed a mos s a ions and dep hs
(Table 1). Seawa e samples o TA we e collec ed a e
pH samples in 600 mL bo osilica e bo les ollowing s an-
da d p ocedu es. Samples we e le a oom empe a u e in
he da k un il analysis a a maximum o 48h a e collec-
ion. TA was measu ed by i a ion wi h 0.1 N hyd ochlo-
ic acid dispensed wi h an au oma ic po en iome ic i a o ,
Ti ando Me ohm®, p o ided wi h a combina ion glass elec-
ode coupled wi h a empe a u e p obe. The elec ode was
s anda dized using a 4.41 pH a ala e bu e made in CO2-
ee seawa e . The TA accu acy was assessed wi h CO2CRM
(ba ch no. 170, p o ided by And ew G. Dickson, UCSD) In
addi ion o he CRM calib a ion, a d i con ol was con-
duc ed by analyzing subs anda d seawa e (big olume o
seawa e s o ed in he da k, as o DIC) a he beginning and
a he end o he analysis session. Each sample was measu ed
wice and he mean alue is epo ed, wi h he mean s anda d
de ia ion o all duplica e di e ences being 0.6 µmolkg−1.
In addi ion, ypical ep oducibili y analysis we e pe o med
om samples collec ed om he same Niskin bo le a di e -
en s a ions along he c uise. The TA p ecision is es ima ed
o be 1 µmolkg−1and he accu acy 2µmolkg−1.
3.8.4 CO2−
3
The CO2−
3ion concen a ion was de e mined spec opho o-
me ically ollowing By ne and Yao (2008) inco po a ing he
ecen imp o emen s by Pa sa as e al. (2015), a selec ed
s a ions and dep hs (Table 1). Samples o CO2−
3we e col-
lec ed a e TA ollowing he same p ocedu e as o pH bu
wi hin cylind ical op ical qua z 10cm pa h leng h cu e es.
The cells we e s abilized a 25◦C o 1 h be o e he analysis
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