bromocarbons in the tropical coastal and open ocean ... · 8138 m. s. mohd nadzir et al.:...

Atmos. Chem. Phys., 14, 8137–8148, 2014www.atmos-chem-phys.net/14/8137/2014/doi:10.5194/acp-14-8137-2014© Author(s) 2014. CC Attribution 3.0 License.

Bromocarbons in the tropical coastal and open ocean atmosphereduring the 2009 Prime Expedition Scientific Cruise (PESC-09)

M. S. Mohd Nadzir1,3,4,*, S. M. Phang3, M. R. Abas1,3, N. Abdul Rahman1,3, A. Abu Samah2,3, W. T. Sturges4,D. E. Oram4,5, G. P. Mills4, E. C. Leedham4, J. A. Pyle5,7, N. R. P. Harris5, A. D. Robinson5, M. J. Ashfold5,** ,M. I. Mead5,*** , M. T. Latif 8,9, M. F. Khan8, A. M. Amiruddin 6, N. Banan8, and M. M. Hanafiah9

1Environmental Research Group, Department of Chemistry, University Malaya, 50603 Kuala Lumpur, Malaysia2National Antarctic Research Centre, IPS Building, University Malaya, 50603 Kuala Lumpur, Malaysia3Institute of Ocean & Earth Sciences, C308 IPS Building, University Malaya, 50603 Kuala Lumpur, Malaysia4Centre for Ocean and Atmospheric Sciences, School of Environmental Sciences, University of East Anglia,Norwich, NR4 7TJ, UK5Centre for Atmospheric Science, Department of Chemistry, University of Cambridge, Lensfield Road,Cambridge, CB2 1EW, UK6Department of Environmental Management, Faculty of Environmental Studies, Universiti Putra Malaysia,43400 Serdang, Selangor, Malaysia7National Centre for Atmospheric Science, UK8Centre for Tropical Climate Change System (IKLIM), Institute for Climate Change, Universiti Kebangsaan Malaysia,43600 Bangi, Selangor, Malaysia9School of Environmental and Natural Resource Sciences, Faculty of Science and Technology,Universiti Kebangsaan, Malaysia* now at: School of Environmental and Natural Resource Sciences, Faculty of Science and Technology,Universiti Kebangsaan Malaysia** now at: School of Biosciences, University of Nottingham Malaysia Campus, Jalan Broga, 43500 Semenyih,Selangor Darul Ehsan, Malaysia*** now at: Institute of Ocean & Earth Sciences, C308 IPS Building, University Malaya, 50603 Kuala Lumpur, Malaysia

Correspondence to:M. S. Mohd Nadzir (mailto:[email protected])

Received: 28 October 2013 – Published in Atmos. Chem. Phys. Discuss.: 13 January 2014Revised: 19 June 2014 – Accepted: 24 June 2014 – Published: 14 August 2014

Abstract. Atmospheric concentrations of very short-livedspecies (VSLS) bromocarbons, including CHBr3, CH2Br2,CHCl2Br, CHClBr2, and CH2BrCl, were measured in theStrait of Malacca and the South China and Sulu–Sulawesiseas during a two-month research cruise in June–July 2009.The highest bromocarbon concentrations were found in theStrait of Malacca, with smaller enhancements in coastal re-gions of northern Borneo. CHBr3 was the most abundantbromocarbon, ranging from 5.2 pmol mol−1 in the Strait ofMalacca to 0.94 pmol mol−1 over the open ocean. Otherbromocarbons showed lower concentrations, in the rangeof 0.8–1.3 pmol mol−1 for CH2Br2, 0.1–0.5 pmol mol−1 forCHCl2Br, and 0.1–0.4 pmol mol−1 for CHClBr2. There was

no significant correlation between bromocarbons and in situchlorophyll a, but positive correlations with both MODISand SeaWiFS satellite chlorophylla. Together, the short-lived bromocarbons contribute an average of 8.9 pmol mol−1

(range 5.2–21.4 pmol mol−1) to tropospheric bromine load-ing, which is similar to that found in previous studies fromglobal sampling networks (Montzka et al., 2011). Statisticaltests showed strong Spearman correlations between bromi-nated compounds, suggesting a common source. Log–logplots of CHBr3/CH2Br2 versus CHBr2Cl/CH2Br2 show thatboth chemical reactions and dilution into the backgroundatmosphere contribute to the composition of these halocar-bons at each sampling point. We have used the correlation to

Published by Copernicus Publications on behalf of the European Geosciences Union.

8138 M. S. Mohd Nadzir et al.: Bromocarbons in the tropical ocean atmosphere during PESC 09

make a crude estimate of the regional emissions of CHBr3and to derive a value of 32 Gg yr−1 for the Southeast (SE)Asian region (10◦ N–20◦ S, 90–150◦ E). Finally, we note thatsatellite-derived chlorophylla (chl a) products do not alwaysagree well with in situ measurements, particularly in coastalregions of high turbidity, meaning that satellite chla may notalways be a good proxy for marine productivity.

1 Introduction

In recent years there has been a growing interest in the roleof short-lived halocarbons in atmospheric chemistry, in par-ticular their potential involvement in stratospheric ozone de-pletion. The term very short-lived substances (VSLS) hasbeen used to represent halogen-containing compounds withlifetimes of less than six months (WMO, 2007). Bromine-containing VSLS and their atmospheric degradation prod-ucts are believed to account for around a quarter of thetotal bromine entering the lower stratosphere (Dorf et al.,2006; Salawich et al., 2006; Montzka et al., 2011), and con-tribute to the “missing” bromine (6 pmol mol−1, range 3–8 pmol mol−1) required for the levels of inorganic bromineBry and BrO measured in the stratosphere (Montzka et al.,2011).

The main brominated VSLS identified to date include bro-moform (CHBr3), dibromomethane (CH2Br2), dichlorobro-momethane (CHCl2Br), dibromochloromethane (CHClBr2)

and bromochloromethane (CH2BrCl). Biogenic emissionsfrom the oceans have been identified as one of the main natu-ral sources where organisms such as macroalgae (seaweeds)and microalgae (phytoplankton) can release large quanti-ties of halocarbon gases into the atmosphere (Sturges et al.,1993; Moore et al., 1996; Laturnus and Adams, 1998). Pre-vious ship and coastal measurements have collected bromo-carbon data for many different global regions, summarised inMontzka et al. (2011). These studies show large temporal andspatial variability in both seawater and atmospheric concen-trations, emphasising the importance of localised emissionsof these gases.

Because of their short atmospheric lifetimes, the regionwhere VSLS are emitted into the atmosphere is significant,and their O3 depletion potentials (ODPs) vary accordingly(Ko et al., 2003). Tropical regions are believed to be the mostimportant location for rapid transport of air from the sur-face to the upper troposphere and lower stratosphere. In thetropics, deep convection provides a major pathway for rapidtransport of insoluble gases from the lower to the upper tro-posphere. Importantly, such convective transport appears tobe particularly strong over the western Pacific (Gettelman etal., 2002; Fueglistaler et al., 2004). Furthermore, the warm,shallow waters of the tropical warm pool make them po-tentially important source regions for biologically producedhalocarbons. Therefore, this region has the potential to sup-

ply a portion of the “missing”∼ 6 pmol mol−1 of bromine,thought to be related to VSLS, to the stratosphere.

Yokouchi et al. (1997) were the first to report at-mospheric bromocarbon measurements in the Strait ofMalacca and the South China Sea. During a cruise be-tween Japan and the Bay of Bengal, they measured meanconcentrations of 0.77 pmol mol−1 (max 1.42 pmol mol−1)and 1.2 pmol mol−1 (max 7.1 pmol mol−1) for CH2Br2 andCHBr3 respectively. The highest levels were seen in harbourregions of Singapore and Penang, and the authors suggesteda link between high CHBr3 concentrations and high chloro-phyll a (chl a), and the influence of algal sources. During acruise in the South China Sea, Quack and Suess (1999) ob-served mean ambient air concentrations for bromoform of1.2 pmol mol−1 (range 0.38–10.6 pmol mol−1).

A second cruise reported in Yokouchi et al. (1997)was made in the western Pacific (Japan–southeastern Aus-tralia), where atmospheric mixing ratios were observed inthe range of 0.13–2.9 pmol mol−1 for CHBr3 and 0.14–1.58 pmol mol−1 for CH2Br2. More recently, Yokouchi etal. (2005) reported a larger range of bromocarbon con-centrations, with CHBr3 ranging from ∼ 1 pmol mol−1

over the open ocean to∼ 40 pmol mol−1in the vicinity oftropical islands in the western Pacific region. Butler etal. (2007a) collected data from seven open ocean cruisesspanning a ten-year period, covering much of the world’soceans. Their tropical air mean mixing ratios for CHBr3and CH2Br2 were 1 pmol mol−1 (0.4–2.1 pmol mol−1) and0.9 pmol mol−1 (0.6–1.3 pmol mol−1) respectively.

Despite these measurements collected over the last twodecades, the seas and coastlines of SE Asia are still vastlyunder-represented. This knowledge gap introduces uncer-tainties into our understanding of the global distributionsand fluxes of bromocarbons and therefore into our abilityto predict future changes in global fluxes and their impacton stratospheric ozone and climate. Pyle et al. (2011) re-ported measurements of bromocarbons from two land-basedsites in Borneo covering 3 weeks in June and July 2008. Thecoastal measurements were characterised by large variabil-ity, from a background of 2 to 5 pmol mol−1 of CHBr3 tooccasional measurements of hundreds of pmol mol−1. Mea-surements around the island were generally much lower andless variable, more consistent with a background of about1 pmol mol−1. The data were used to make an estimate of theregional emission strength of CHBr3, which, depending onassumptions, ranged between 21 and 50 Gg yr−1 in SE Asia(10◦ N × 20◦ S, 90◦ E to 160◦ E). For the purpose of compari-son we will also consider tetrachloroethylene (C2Cl4), whichhas predominantly industrial uses as a metal degreasing sol-vent, and dry cleaning, and can be considered to be a tracerof anthropogenic activity (Pyle et al., 2011).

How representative these Borneo measurements are of thewhole SE Asia region is an important question, and one thatwas addressed by thePrime Expedition Scientific Cruisein2009 (PESC-09). Selected halocarbons, including the five

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M. S. Mohd Nadzir et al.: Bromocarbons in the tropical ocean atmosphere during PESC 09 8139

bromomethanes detailed above, were measured in air sam-ples collected in three different areas: the Strait of Malacca(SM), the South China Sea (SCS) and the Sulu–Sulawesiseas (SSS). Samples were collected at both coastal and openocean locations, sometimes close to the sites mentioned inPyle et al. (2011). The cruise and measurement details arepresented in Sect. 2. Results are presented and discussed inSect. 3.

2 Measurements

2.1 Cruise details

The PESC-09 cruise was conducted by the Malaysian RoyalNavy and the Malaysian Ministry of Science and Technol-ogy Innovation (MOSTI), and involved local government,private research agencies and public universities in Malaysia.The vessel used was the Kapal Diraja (Royal Ship) Peran-tau, which is designed and equipped for hydrographic sur-veying and for conducting meteorological and oceanographicobservations. The cruise started from Port Klang (2◦57′ N,101◦20′ E) in the Strait of Malacca on 18 June and endedat Kota Kinabalu (6◦11′ N, 116◦10′ E) on 31 July. Thesepaths were separated into four different legs: leg one (PortKlang–Labuan); leg two (Labuan–Layang–Layang Island–Kota Kinabalu); leg three (Kota Kinabalu–Tawau); and legfour (Tawau–Kota Kinabalu). Figure 1 shows the ship’s routetogether with the location of the 27 air-sampling stations.

During the seven-week cruise, several different oceanic re-gions were covered, including SM, SCS and SSS and coastalregions of western and northern Borneo. Mangrove forest,sea grass beds and coral reefs dominate much of the coast-line and, in northern Borneo in particular, there are areas ofcultivated macroalgal beds along the coastline at sites such asSemporna, Kunak and Lahad Datu. The sampling locationswere chosen to represent a variety of coastal and open oceansites.

2.2 Sampling and measurements

Air was sampled through a 1/4′′ OD PFA tube located onthe upper deck, with the inlet∼ 10 m above the ocean sur-face and adjusted at each sampling time to face the prevail-ing wind. Air was pumped into a pre-evacuated 3 L canis-ter (Restek SilcoCan™) using a compact, battery-operateddiaphragm pump (Rasmussen) until the canisters were ap-proximately two atmospheres above ambient pressure (ap-proximately five minutes of sampling). Canisters were filledand vented at least three times, before a final fill which waskept for analysis. A total of 27 air samples was collected dur-ing the cruise, and these were shipped to the University ofEast Anglia (UK) for halocarbon analysis by GC–MS (gaschromatography–mass spectroscopy).

The samples were processed within four months of collec-tion using a commercial thermal desorption system (Markes

Figure 1. Sampling locations overlaid with SeaWiFS chla duringPESC 2009 (labels: the diamond is the 1st leg, the square is the 2ndleg, the circle is the 3rd leg, and the triangle is the 4th leg).

UNITY™/Air Server). The analytical technique was simi-lar to that described by Worton et al. (2008). Air samples(1000 mL) were dried with a Nafion™ counter-flow dryerprior to collection and pre-concentration on a two-bed adsor-bent trap at−15◦C. The desorbed analytes were separated ona capillary column (Restek 100m× 0.32mm RTX 102) us-ing a temperature programme of 30◦C (2 min), 8◦C min−1

to 150◦C (16 min), and 20◦C min−1 to 220◦C (5 min). Themass spectrometer was operated in negative ion, chemi-cal ionisation (NICI) mode using methane (≥ 99.99 %) asthe reagent gas. The quadrupole detector was run in sin-gle ion mode, monitoringm/z 35/37 for chlorinated,m/z79/81 for brominated andm/z 127 for iodinated compounds.Samples were normally analysed twice and referenced to aworking standard. The working standard was an aluminiumcylinder containing dried ambient air at high pressure. Themole fractions of halocarbons in the working standard weredetermined by repeat comparison to calibrated gas stan-dards supplied by NOAA-ESRL in electropolished stain-less steel canisters (Essex Industries). These comparisons

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are performed periodically and allow an assessment of anypotential changes in the absolute mole fractions of halocar-bons in our working standard over time. From comparisonsto three separate NOAA standards, SX-3546 (comparisonperformed in 2008), SX-3570 (2010), and SX-3568 (2012),we believe the concentration of CHBr3 in the working stan-dard has declined by approximately 40 % over the periodOctober 2008–September 2012, whilst that of CH2Br2 hasremained essentially unchanged (1.23± 0.07 pmol mol−1, or5.6 %; 1σ). NOAA calibration data for the three mixed bro-mochloromethanes were only available for the 2010 and2012 comparisons, but our analysis shows that the concentra-tions of CH2ClBr and CHClBr2 in the working standard haveremained approximately constant (0.28± 0.004 pmol mol−1,or 1.5 % and 1.18± 0.04 pmol mol−1; 3.2 % respectively),whilst that of CHCl2Br may have increased by around 15 %(1.56± 0.17 pmol mol−1, or 10.6 %). The calibration factorsapplied to the PESC-09 data have been time corrected as ap-propriate. This drift analysis makes the underlying assump-tion that the five bromocarbons are stored reliably in the Es-sex stainless steel cylinders.

The mole fractions reported here are on the latest NOAAscales for CH2Br2 (2004) and CHBr3 (2003), and on a pre-liminary NOAA scale for CH2BrCl, CHBrCl2 and CHBr2Cl(Brad Hall, personal communication). The uncertainty in theabsolute mole fractions in the working standard, based oncombined uncertainties associated with the standard com-parisons and NOAA’s stated uncertainties, was± 6. 5% forCH2Br2, ± 7.1 % for CHBr3,± 7.5 % for CH2ClBr,± 5.9 %for CHCl2Br, and± 6.8 % for CHClBr2. The mean analyti-cal precision of the actual PESC-09 samples was < 3 % forCH2Br2 and CHBr3, < 5% for CHBrCl2 and CHBr2Cl, and∼ 15 % for CH2BrCl, due to its low abundance and low re-sponse in NICI.

Chl a in the surface seawater was measured using theKapal Diraja (KD) Perantau’s in situ fluorometer attachedto a Sea-Bird SBE-911plus CTD (conductivity, temperature,depth) system at all 27 sampling locations. The CTD equip-ment was operated together with a package consisting ofa 24-place, 10 L rosette frame, a 24-place water sampler(SBE32) and a 24 10 L Niskin bottle sampler. This pack-age was deployed at all stations. Several fluorometers, tur-bidity sensors and pH measurements were attached to theCTD. The CTD instrument was run and calibrated automati-cally at each station before sampling. The chla concentrationwas measured from 1 m to 20 m depths, with 5 m intervals.Readings were taken at the sea surface at approximately 1 min depth and have been compared to satellite-derived chla

data from SeaWIFS (Sea-viewing Wide Field-of-view Sen-sor) and MODIS (Moderate Resolution Imaging Spectrora-diometer). Chla derived from ocean colour measurementsmade during overpasses of the SeaWIFS and Aqua-MODISsatellite sensors were used to determine apparent chla valuesin the 9× 9 km grid square nearest to each sampling point.The corresponding monthly average chla values (i.e. those

Figure 2. Bromocarbon mixing ratios for each station during PESC2009.

for either June or July) were used, obtained from the NASAGoddard “Giovanni” online database (http://oceancolor.gsfc.nasa.gov/SeaWiFS/). Shorter (e.g. eight-day) averaging peri-ods are available, but were found to be insufficient for fullcoverage of the cruise track, given the width of the view-ing swath, the number of missing data on several overpasses,and differences between satellite sensors in ocean colour-derived chla. There is a substantial difference in both thetemporal and spatial scales between the monthly averagedand 9× 9 km grid box-averaged satellite measurements andthe near-instantaneous in situ “spot” measurements. As anindication of the level of uncertainty (at least that related tospatial scales), the standard deviation of satellite-determinedchl a was calculated for the eight to ten grid boxes surround-ing and including the target grid box, depending on the valuesat each location (negative values were not considered).

3 Results and discussion

In the following sections we will, first, present an overviewof the halocarbon data collected during PESC-09 (Sect. 3.1).We then discuss possible causes of any observed variability,focussing on an analysis of air parcel trajectories and in situmeasurements of chla, which are a possible proxy for bio-logical activity (Sect. 3.2). In Sect. 3.3 we explore correla-tions between the measured species and provide a rough es-timate of regional bromoform emissions. Finally (Sect. 3.4),we use the data to investigate the potential contribution ofVSLS to stratospheric bromine loading.

3.1 Halocarbon measurements

Mean and standard deviation of the measured halocar-bon concentration at each site are given in Table 1 alongwith some comparison to data from the literature. Fig-ure 2 shows the concentrations of brominated compounds(CHBr3, CH2Br2, CHBr2Cl, CHBrCl2 and CH2BrCl) at eachof the cruise sampling sites, whose locations are marked inFig. 1. The most abundant bromine compound was CHBr3,with mean concentrations from around 1 pmol mol−1 to


http://oceancolor.gsfc.nasa.gov/SeaWiFS/

http://oceancolor.gsfc.nasa.gov/SeaWiFS/


Table 1.Mean, standard deviation (in brackets) and range (in bold) values of the measured halocarbon concentrations in this work and valuesfrom the literature based on tropical ocean areas (n.m.: not mentioned).

Bromocarbon mixing ratios

Area Author CHBr3Mean (std)range

CHBr2ClMean (std)range

CH2Br2Mean (std)range

CHBrCl2Mean (std)range

CH2BrClMean (std)range

Chl a

(mg m−3)(std)

Turbidity(FTU)

Strait of Malacca

Coastal This study 3.69 (1.54)1.85–5.25

0.32 (0.09)0.19–0.39

1.38 (0.37)1.05–1.92

0.12 (0.02)0.19–0.39

0.12 (0.04)0.1–0.14

0.19 (0.3) 3.33(1.22)

South China Sea

Open ocean This study 1.51 (0.4)1.07–2.02

0.21 (0.05)0.15–0.27

1.01 (0.19)0.88–1.29

0.22 (0.07)0.17–0.32

0.10 (0.01)0.09–0.11

0.17 (0.09) 0.19(0.07)


0.15 (0.08)0.12–0.2

0.90 (0.09)0.82–1.02

0.18 (0.03)0.15–0.22

0.10 (0.03)0.07–0.15

0.22 (0.12) 0.15(0.07)

Sulu–Sulawesiseas


0.23 (0.08)0.15–0.44

1.04 (0.16)0.89–1.36

0.3 (0.08)0.22–0.52

0.15 (0.04)0.12–0.28

0.32 (0.2) 1.54(0.92)

Previous study over the tropical ocean

Southeast Asia100–105◦ E

Youkouchi et al. (1995) 1.2 (n.m.)0.3–7.0

0.77 (n.m.)0.38–1.42

Western Pacific43◦ N, 150◦ E and4◦ N, 113◦ E

Quack and Suess (1994) 1.2 (n.m.)0.38–10.67

0.2 (n.m.)0.07–1.34

0.28 (n.m.)0.08–2.96

San CristobalIsland(Loberia)

Yokouchi et al. (2005) 14.2 (10.1)4.2–43.6

1.5 (1.0)0.5–4.1

3.2 (1.5)1.8–7.6

Christmas Island(Topono)

Yokouchi et al. (2005) 23.8 (10.7)16.3–31.4

2.0 (0.7)1.5–2.4

3.0 (1.0)2.3–3.7

Java Island Yokouchi et al. (2005) 0.9 (0.4)0.4–1.6

0.2 (0.2)0.1–0.6

0.9 (0.2)0.6–1.5

Pacific Equator Yokouchi et al. (2005) 1.9 (0.9)0.8–3.5

0.3 (0.1)0.1–0.6

1.3 (0.5)0.2–0.5

more than 5 pmol mol−1 (mean = 1.85 pmol mol−1, max= 5.2 pmol mol−1). Most measurements are between 1and 2 pmol mol−1. The mean mixing ratio of CH2Br2 was1.23 pmol mol−1 (max = 2.21), with the minor speciesCHBr2Cl, CHBrCl2 and CH2BrCl having mixing ratios inthe mean 0.1 to 0.9 pmol mol−1. For the anthropogenictracer C2Cl4, mixing ratios varied only between 0.9 and1.0 pmol mol−1. The PESC-09 measurements are generallywithin the range of previous measurements in tropical re-gions.

3.2 Regional analysis

3.2.1 Strait of Malacca (stations 1–4)

PESC-09 took place during the Southwest Monsoon (SWM),when sea surface temperatures are slightly warmer (28–32◦C, May/June) than in the Northwest Monsoon (NWM)(25–29◦C, December/January). Tan et al. (2006) report thatchl a in the Strait of Malacca shows seasonal variability,with concentrations increasing by as much as a factor of 2(0.57 mgm−3 in August and 1.38 mgm−3 in January 1992–2002 on a monthly average) during the NWM compared tothe SWM.

The highest concentrations of CHBr3 were observed atthe beginning of the cruise in the Strait of Malacca (SM).The mean concentration in samples 2–4 was 4.4 pmol mol−1,which is similar to the levels in the same region reported byYokouchi (1997). The enhanced levels may be related to thehigh population of macro and micro algae such as phyto-plankton and seaweed in coastal areas, especially in the re-gion of 1–2◦ N, 102–103◦ W. Previous studies on chla in theSM were influenced by nutrient input from rivers of Sumatra(Tan et al., 2006). CH2Br2, CHCl2Br, CHClBr2 and CHCl3were also enhanced in samples 2–4, which is indicative ofsimilar sources.

3.2.2 South China Sea (stations 5–14)

Measurements in the SCS show fairly uniform and relativelylow mixing ratios for all brominated compounds. For ex-ample, the mean values for CHBr3, CH2Br2 and CHBr2Clwere 1.46, 1.12 and 0.35 pmol mol−1 respectively, with nosignificantly enhanced values. The prevailing wind directionfor most samples collected along this section of the cruisewas westerly, so the influence of any local coastal emissionswould likely be low.



3.2.3 Sulawesi and Sulu seas (stations 15–27)

Slightly higher concentrations of bromocarbons were ob-served during the cruise through the SSS, especially at sta-tions 22 and 24, where CHBr3 concentrations were 2.37 and2.60 pmol mol−1, respectively. During this period the shippassed near to coastal sites at Semporna (station 22), Ku-nak (19, 20, 21, 27) and Tawau (24, 26). The coastal areasnear Semporna and Kunak have significant seaweed biomass,with cultivatedKappaphycusand Eucheumaat Semporna,andSargassumand other brown algae at Kunak. Samples 17and 21 had slightly elevated levels of C2Cl4, suggesting apossible influence from local anthropogenic sources.

Pyle et al. (2011) measured CHBr3 concentrations at Ku-nak ranging from a typical background of 2–5 pmol mol−1,but with high concentrations of up to 60 pmol mol−1 (the lat-ter were attributed to measurement very close to local emis-sions). During their short measurement period in July 2008,the air flow was predominantly from the southeast, with backtrajectories showing air travelling from northern Australia,over the Timor and East Java seas and up the eastern coast ofBorneo. The authors speculated that these are areas of highbiological activity, with both the warm ocean and extensivecoastline providing significant sources of halocarbons. De-spite similar air mass back trajectories and sampling in sim-ilar locations, we did not measure the very high levels ofCHBr3 reported by Pyle et al. (2011). For example, at sta-tion 27, backward trajectories did not indicate that air flowhad passed any seaweed or high-nutrient area.

3.3 Drivers of variability

The data collected during PESC-09 show relatively smallvariability, consistent with the ship data reported by Yok-ouchi et al. (1997) over the western Pacific and SE Asia(see Table 1). For example, Yokouchi observed mixing ra-tios of CHBr3 of 0.32 to 7.1 pmol mol−1, which is similar toour study, with a range of 1.85–5.25 pmol mol−1 for CHBr3.This contrasts with the study of Yokouchi et al. (2005) overthe western Pacific and Java Island, who observed high mix-ing ratios with a range of 16.3 to 31.4 pmol mol−1 at Christ-mas Island, and 4.2 to 43.6 pmol mol−1 at San Cristobal Is-land. Pyle et al. (2011) also observed high mixing ratios ofCHBr3 in Malaysian Borneo (near to stations 21 and 27 inthis study), with a range of 2 to 60 pmol mol−1. It seemslikely that these latter studies both included data collectedclose to emission sources.

Atmospheric variability is driven by various factors, in-cluding wind direction, atmospheric lifetime, proximity tolocal sources and temporal variation in flux rates. Changes inVSLS emissions could arise from a number of complex fac-tors. Emissions of VSLS are predominantly biogenic, withthe ocean being the most important source (Baker et al.,2000; Quack et al., 2004). Proximity to local seaweed beds(including seaweed farms) is likely to be an important influ-

Figure 3. Ten-day air distribution backward trajectories calculatedfrom the NOAA HYSPLIT model for each selected station.

ence in coastal regions. In the case of microalgae, their abun-dance and distribution in seawater are affected by nutrientsupplies and sea surface temperatures, while sea–air fluxes ofVSLS are determined by meteorological parameters includ-ing wind speed. Chla can be used as a simple proxy for bio-logical activity, possibly producing halocarbons, which maybe emitted into the atmosphere, depending on concentrationsand wind speed.

3.3.1 Meteorological variability

A major factor controlling the variability of the halocarbonconcentrations during the cruise is the wind direction. Figure3 shows selected ten-day air mass back trajectories for sevenof the cruise sampling locations calculated from the NOAAHYSPLIT model (R. R. Draxler and G. D. Rolph, HYSPLIT– Hybrid Single-Particle Lagrangian Integrated Trajectory),available athttp://www.arl.noaa.gov/ready.html). In all casesthe large-scale structure is consistent. Air masses arrivingat the sampling locations originated from the southeast andhave likely been influenced by emissions from shallow, warmseas, including the South Java Sea. There is therefore likelyto be little variability associated with transport from differentlarge-scale emission regions, although local emissions closeto the sampling locations could still be important in drivinglocal variability. For example, the trajectories arriving at site22, near Sipadan Island, or at station 19, near Kunak, are verylikely to have been influenced by the seaweed beds in thatarea. A similar conclusion was reached by Pyle et al. (2011)based on their coastal Kunak measurements in June 2008,made one year earlier than the PESC-09 cruise, and the ori-gins of the measured air masses were very similar in bothyears.


http://www.arl.noaa.gov/ready.html


Figure 4.chl a concentrations from the satellite data plotted againstin situ chla. The solid symbols represent samples where turbiditywas > 0.5 FTU, and open symbols for turbidities < 0.5 FTU. Theline is a linear fit to the lower turbidity samples.

3.3.2 Biological activity

Chl a was also measured at 60 sites, including 27 sites wherehalocarbons are measured during the cruise, both in situ fromthe ship and remotely from satellite sensors. We comparethe chl a measurements to the halocarbon data to explorepossible biological drivers of variability. Figure 1 plots themonthly average chla across the region from SeaWiFS forJune 2009 overlaid with the sampling stations. High chla

levels are commonly observed along the coastlines, seem-ingly indicating high phytoplankton abundance. Indeed, highsatellite-derived chla values were evident in the Strait ofMalacca, where the highest CHBr3 was measured. However,a plot of ocean colour-derived chla from the two satellitesensors versus in situ chla (Fig. 4) shows significant dis-agreement between the remotely sensed and in situ measure-ments. The standard deviations from the target grid box andthose surrounding it are in the range of 1.1 to 32.4 mgm−3

for MODIS and 0.1 to 18.2 mgm−3 for SeaWiFS.In Fig. 4, the filled symbols denote samples in which the

turbidity was > 0.5 FTU (Formazin turbidity unit), whereasthe open symbols denote low turbidity (< 0.5 FTU). It is ap-parent that the low turbidity samples display a relativelycompact relationship between remotely sensed and in situchl a, and with absolute values that are in good quantitativeagreement. Indeed, a linear regression on the lower turbiditysamples yields a gradient of 1.0 (standard error of 0.1) andan r2 value of 0.88. The points that do not follow the posi-tive linear regression line are characterised by satellite chla

concentrations greater than 1 mg m−3 and turbidities greaterthan 0.5 FTU, implying that the satellite sensors overesti-mate chla under such conditions. Indeed, the in situ mea-surements showed that ship-board measurements of chla arelower than those made in the open ocean. We reiterate (re-fer back to Sect. 2.2) that there are difficulties in comparingcoarse satellite data to in situ measurements, but believe thatthis type of comparison still provides valuable informationfrom a data-sparse region.

Plots of bromocarbon air concentration versus satellite chla concentration (Fig. 5) show a positive correlation, withthe highest mixing ratios of CHBr3 and CH2Br2 associatedwith above-average chla values (> 5 mgm−3) for the MODISand SeaWiFS satellites. Both satellite chla products showr2 values > 0.6 against CHBr3 and CH2Br2 (also CHBr2Clfor MODIS), but other species show little correlation forboth satellite chla products. In situ chla concentrationsshow a negative correlation for all bromocarbons species,with r2

= −0.26 (p > 0.01) andr2= −0.21 (p > 0.01) for

CHBr3 and CH2Br2, respectively (see Fig. 5). The exact rea-son for the weak correlation of the bromocarbons and the insitu chla data is unclear.

The above finding is not necessarily surprising even ifphytoplankton are a source of such gases, since a connec-tion between bromocarbons measured in the marine atmo-spheric boundary layer and sub-surface biology may be de-pendent on other factors including wind speed. Furthermore,the observed halocarbon concentrations might originate overa wide geographic area and are not necessarily driven solelyby localised emissions. In this context, satellite-derived chla, also providing information from a wider area, may poten-tially be more relevant than in situ measurements. Althoughturbidity measurements in the Strait of Malacca (average of3.3 FTU) were significantly higher than those in the SouthChina Sea (average of 0.3 FTU; Table 1), coinciding withhigh CHBr3, the turbidity was almost as high close to landnear Semporna (average of 2.1 FTU for stations 24–27), butwith little evidence of substantially enhanced halocarbons inthe latter region due to the lower marine productivity, espe-cially in the coastal and open ocean regions of SCS (Fig. 1).We conclude that halocarbon concentrations are generallysomewhat higher close to land and also higher in the Strait ofMalacca; a connection to the coastal zone is thus suspected,but there is little evidence to connect this directly to openocean microorganisms.

3.4 Emission ratios

Significant correlations between brominated halocarbonshave been observed in coastal air measurements, suggestingthat these gases have come from the same sources (Yokouchiet al., 2005; O’Brien et al., 2009; Carpenter et al., 2009).Several studies have exploited these correlations to explorethe possible source strengths of the individual species. Car-penter et al. (2003), Yokouchi et al. (2005) and O’Brien et



Figure 5: Monthly June-July 2009 in situ and satellite chl-a concentration as a function of

VSLS bromocarbons mixing ratios a) CHBr3, b) CH2Br2 c) CHBr2Cl d) CHBrCl2 and e)

CH2BrCl.

(a)

0.8 1.0 1.2 1.4 1.6 1.8 2.0

0

1

2

3

4

5

6

7

r2=0.72, p>0.001

r2=0.66, p<0.01

In s

itu

+ s

ate

llite

ch

l-a

co

nce

ntr

atio

n (

mg

m)

-3

CH2Br

2 mixing ratio (pmol mol

-1)

r2=-0.21, p>0.1

(b)

0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45

0

1

2

3

4

5

6

7

r2=0.62, p<0.001

r2=-0.11, p>0.1

r2=0.49, p>0.01

CHBr2Cl mixing ratio (pmol mol

-1)

In s

itu

+ s

ate

llite

ch

l-a

co

nce

ntr

atio

ns (

mg

m)

-3

0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55

0

1

2

3

4

5

6

7

In s

itu

+ s

ate

llite

ch

l-a

co

nce

ntr

atio

n (

mg

m)

-3

r2=0.39, p>0.1

r2=0.37, p>0.01

CHBrCl2 mixing ratio (pmol mol

-1)

r2=0.13, p>0.1

(d)

1 2 3 4 5 6

0

1

2

3

4

5

6

7

r2=-0.26, p>0.1

r2=0.62, p<0.001

r2=0.85, p<0.0001

In s

itu

+ s

ate

llite

ch

l-a

co

nce

ntr

atio

ns (

mg

m)

-3

CHBr3 mixing ratio (pmol mol

-1)

Bromocarbons vs. MODIS

Bromocarbons vs. SeaWiFS

Bromocarbons vs.. in situ

Linear fit in situ

Linear fit SeaWiFS

Linear fit MODIS

(c)

0.05 0.10 0.15 0.20 0.25 0.30

0

1

2

3

4

5

6

7

In s

itu

+ s

ate

llite

ch

l-a

co

nce

ntr

atio

n (

mg

m)

-3

CH2BrCl

mixing ratio (pmol mol

-1)

r2= 0.06, p>0.1r

2= 0.11, p>0.1

r2= 0.41, p>0.1

(e)

Figure 5. Monthly June–July 2009 in situ and satellite chla concentrations as a function of VSLS bromocarbon mixing ratios:(a) CHBr3,(b) CH2Br2, (c) CHBr2Cl, (d) CHBrCl2, and(e)CH2BrCl.

al. (2009) all show that a log–log plot of CH2Br2/CHBr3versus CHBr3 often shows a straight line, with the ratioCH2Br2/CHBr3 increasing with decreasing CHBr3. Atmo-spheric ratios of CH2Br2/CHBr3 are often interpreted in thelight of their differing atmospheric lifetimes, which are about26 days for CHBr3 and 120 days for CH2Br2 (Montzka et

al., 2011). The relationship between CHBr3 and other some-what longer-lived brominated halocarbons such as CHBr2Clalso showed similar patterns; for example, CHBr2Cl/CHBr3would be higher at a lower concentration of CHBr3. SinceCHBr3 has the shorter lifetime of the two species, an increasein the ratio would be consistent with more aged air masses in



Figure 6: Plot for correlations of CH2Br2 and CHBr2Cl versus CHBr3 concentrations.

1 2 3 4 5 6

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

CH2Br

2

CHBr2Cl

[CH

2B

r 2],[C

HB

r 2C

l] p

mo

l m

ol-1

[CHBr3] pmol mol-1

Figure 6. Plot for correlations of CH2Br2 and CHBr2Cl versusCHBr3 concentrations.

which CHBr3 has been removed at a faster rate. Yokouchiet al. (2005) used the minimum ratio of CH2Br2/CHBr3 todefine the ratio of the emission sources by assuming thatthe emissions came from the common sources and are con-stant on a regional scale. If the global emission of CH2Br2is known, then that of CHBr3 can be inferred. However, theemission ratio for CH2Br2/CHBr3 in the open ocean is dif-ferent to (i.e. higher than) that in coastal areas, and so the as-sumption of a single characteristic seawater ratio is invalid,along with the extrapolation of source strength.

Figure 6 shows the relationships between CH2Br2 andCHBr3 and between CHBr2Cl and CHBr3 for each data set.Correlations are strong between CH2Br2 and CHBr3 (corre-lation coefficientr2

= 0.9), CHBr3 and CHBr2Cl (r2= 0.7),

and CHBr3 and CHBrCl2 (correlation coefficientr2= 0.5)

(not shown in the figure). These variations in correlation areconsistent with the relationships observed in recent studies ofthe strength of emission of these different compounds froma range of Malaysian seaweeds (Leedham et al., 2013; Seh-Lin Keng et al., 2013). Figures 7a and b show the concentra-tion ratios of CH2Br2/CHBr3 and CHBr2Cl/CHBr3 plottedagainst CHBr3 on a log–log scale, with both ratios increas-ing linearly as CHBr3 decreases; CHBr3, with its shorter life-time, is a possible measure of time since co-emission. Thesefigures are consistent with those reported by Yokouchi etal. (2005).

Yokouchi et al. (2005), following McKeen and Liu (1993),used plots of pairs of ratios, e.g. CHBr3/CH2Br2 versusCHBr2Cl/CH2Br2, where CH2Br2 has the longest lifetime,to explore the possible emission strengths of the individualspecies. Making a number of assumptions, in such a plot thelocation of individual points in ratio space is determined bythe emission ratio at an (assumed) common regional sourceand by the ratio of the rates of chemical removal and mixingin the “background” atmosphere. Assuming that the emis-

Figure 7. (a) Log–log plot CH2Br2/CHBr3 and CHBr2Cl/CHBr3against CHBr3, and (b) log–log plots of CHBr3/CH2Br2 againstCHBr2Cl/CH2Br2 for all stations during the Perdana cruise, fol-lowing Yokouchi et al. (2005) and Brinckmann et al. (2011). Thesolid line is the dilution line 1:1 and the solid dashed line is thechemical decay line estimated from the lifetime of the three speciesin the atmosphere. In this case, we have followed the example ofYokouchi et al. (2005) by using the lifetimes of 26 days (CHBr3),69 days (CHBr2Cl) and 120 days (CH2Br2). The decay line thushas a slope of 4.89. The black point at the top of the data setis the point C in Yokouchi et al. (2005), and the grey point isthe point A in the Brinckmann et al. (2011) log–log plots whereCHBr3/CH2Br2 is around 9 and CHBr2Cl/CH2Br2 is around 0.7from Yokouchi et al. (2005), and around 5 for CHBr3/CH2Br2 and0.2 for CHBr2Cl/CH2Br2 from Brinckmann et al. (2011).

sion source strength of one species is known, that of theothers can be obtained using the ratio determined from theplot. Using this method, O’Brien et al. (2009) estimated aglobal emission of bromoform of 823–1404 Gg yr−1 (valuesdepend inter alia on the assumed CH2Br2 emissions) usingdata collected at Cape Verde in June 2006. This emission ismuch higher than estimates in Ko et al. (2003) or in War-wick et al. (2006). However, Pyle et al. (2011) suggest thatit is not reasonable to derive global emission estimates from



regional data for a short-lived species such as bromoform.They showed that data from Borneo could instead only beused to constrain regional emissions.

Using data from the cruise, CHBr3/CH2Br2 is plottedagainst CHBr2Cl/CH2Br2 in Fig. 7b. The left side of the tri-angle is the “dilution line” (the 1:1 slope for mixing intoa zero background) and the “chemical decay line”, definedby the ratio of lifetimes of individual species due to photo-chemistry, is the right-hand line. The intersection of thesetwo lines, a point typically chosen to allow the lines to en-compass the majority of the data, defines the emission ra-tios. Nearly all the data falls into a triangle whose vertexfor CHBr3/CH2Br2 takes a value of 5 (point D in the fig-ure). This is about half the value reported by Yokouchi etal. (2005) and O’Brien et al. (2009), but similar to the re-sult obtained by Brinckmann et al. (2012) based on data col-lected on a recent western Pacific cruise. If we assume thatthis emission ratio of 5 is appropriate for the SE Asian re-gion, (10◦ N to 20◦ S, 90◦ E to 160◦ E, as used by Pyle etal., 2011), and recalling that the air mass histories in thetwo periods of these two studies are quite similar, then wecould derive an emission estimate for CHBr3 from the re-gional CH2Br2 emission. That value is not observationallyconstrained; instead we use the SEA regional CH2Br2 emis-sion from an updated version of the Warwick et al. (2006)inventory (as used by Yang et al., 2014). As before, spa-tially uniform ocean emissions of CH2Br2 are assumed inthe tropics, but emissions are halved, so that the global totalof 57 Gg CH2Br2/yr is more consistent with the recent stud-ies of Liang et al. (2010) and Ordonez et al. (2012). In thatcase, with a SEA CH2Br2 emission of 6.4 Gg yr−1, we obtaina regional emission, based on point D from Fig. 7b, of about32 Gg yr−1 of CHBr3. This value is within the range obtainedby Pyle et al. (2011), who estimated emissions of CHBr3 forthe same area to be between 21 and 50 Gg yr−1. It is alsoconsistent with the recent work of Ashfold et al. (2014), whoestimated a total tropical CHBr3 emission of 225 Gg yr−1;simply scaling this tropical number down (using the ratio ofareas) to the SEA region considered here implies a CHBr3emission of 33 Gg yr−1. Our estimates, and those of Pyleet al. (2011) and Ashfold et al. (2014), are all much lessthan the regional value in Warwick et al. (2006). To be moreconfident about our emission value would require, amongstother things, improved estimates of the CH2Br2 emission.However, the consistency of the calculations does suggestthat useful constraints on regional estimates can be obtainedbased on the McKeen and Liu (1993) plots.

3.5 Total bromine

The cruise data can be used to give an upper limit on theamount of bromine which could potentially reach the strato-sphere, i.e. by summing the measured bromine mixing ra-tios and weighting by the number of bromine atoms. Themean VSLS-derived bromine ([Br]VSLS) in the 27 samples

was 8.9± 3.7 pmol mol−1. There is some regional variabil-ity, as discussed earlier, with SM having the highest [Br]VSLS(mean= 17.8 pmol mol−1) compared to other sampled ar-eas. Of this 8.9 pmol mol−1, CHBr3 contributes∼ 65 % andCH2Br2 25 %. This is similar to results compiled by Montzkaet al. (2011), for which an average total bromine from thesame gases in the tropical marine boundary layer (mostlyfrom open ocean measurements) is given as 8.4 pmol mol−1,with a range of 3.6–13.3 pmol mol−1. With the exceptionof the Strait of Malacca, there does not appear to be alarge regional enhancement of [Br]VSLS in our data, despitethe cruise having taken place mostly within 50 km of thecoast. The data do not suggest that this part of SE Asia isa “hotspot” for emissions.

The [Br]VSLS measured during the PESC-09 cruise arelikely to account for some of the “missing” bromine enter-ing the stratosphere, assuming conservative transport of theconstituent bromine either in the form of the source gas itselfor as brominated product gases.

4 Conclusions

We report in situ halocarbon and ancillary data obtainedduring a research cruise of the Perantau in June and July2009. The cruise covered the Strait of Malacca, the SouthChina Sea and the Sulu and Sulawesi seas. These are warm,shallow ocean areas, and contain conditions likely to sup-port high halocarbon production and emission into the at-mosphere. The region is also important as a location of thestrongest convection; therefore it represents potentially animportant source region for the transport of marine bound-ary layer concentrations of VSLS to the upper troposphereand stratosphere.

Data were collected at 27 sites during the cruise. Highbromoform concentrations (4–5 pmol mol−1) were measuredin the nutrient-rich Strait of Malacca. Otherwise, concen-trations were generally between 1 and 2 pmol mol−1. Thisis consistent with an earlier cruise reported by Yokouchiet al. (1997). Slightly higher concentrations were measuredclose to seaweed farms in Semporna, but nowhere on thecruise did we find very high concentrations similar to thosereported by Pyle et al. (2011) at a coastal site at Kunak, be-lieved to be close to emission sources. Furthermore, thereis no evidence from the cruise data that local emissionsources in this region lead to widespread, elevated concentra-tions (“hotspots”) which might make a contribution to strato-spheric input out of proportion to the area of the region.

Our measurements of other compounds, includingthe less often reported mixed chloro-bromocarbons,are also reasonably consistent with the few other stud-ies in the region (e.g. Quack and Suess, 1999 andYokouchi et al., 1997; see Table 1). Our typical con-centrations of CH2Br2 ∼ 1 pmol mol−1, CHBr2Cl ∼ 0.2–0.4 pmol mol−1, CHBrCl2 ∼0.2–0.3 pmol mol−1 and



CH2BrCl ∼ 0.1–0.2 pmol mol−1 lead to a [Br]VSLS of8.9 pmol mol−1. This is close to values obtained by Salaet al. (2014) from measurements collected in the planetaryboundary layer of the same region during the SHIVAcampaign (7.8 and 9.1 pmol mol−1 using two separateinstruments). The similarity suggests that boundary-layerVSLS mixing ratios in this important region are beginningto be better characterised.

The bromocarbons were well correlated, suggesting com-mon sources. Previously, such relationships were used to ob-tain global emission estimates. For a short-lived gas like bro-moform, with an atmospheric lifetime of∼ 26 days, we donot think this approach is suitable; the footprint sampled bythe cruise is regional at most. Instead, we used an approach asapplied by Yokouchi et al. (2005) to provide a very rough es-timate of the regional (SE Asia) emission ratio of bromoformto dibromomethane of about 5. Using an updated version ofthe Warwick et al. (2006) dibromomethane emissions leadsto bromoform emissions of 32 Gg yr−1 for SE Asia (10◦ Nto 20◦ S, 90◦ E to 160◦ E), which is in reasonable agreementwith the recent estimates from Pyle et al. (2011) and Ashfoldet al. (2014). Many more data, not least on CH2Br2 emis-sions, would be required to confirm this estimate, but the useof species correlations for regional emission estimates looksto be a promising approach.

Chl a was also measured on the cruise. There was littleobvious correlation between this and the measured atmo-spheric halocarbon concentrations. Satellite measurementsof chl a suggested high values in the Strait of Malacca, co-inciding with high turbidity and high halocarbon concentra-tions. However, it seems likely that the satellite data were af-fected by the high turbidity in these waters, and the underwa-ter in situ chla measurements were similar to those observedin the open sea. It seems likely that the higher halocarbonconcentrations in the Strait maybe result from the local influ-ence of the nearby coastal areas and land masses.

The seas around SE Asia are important for a numberof atmospheric processes, including both convection andthe emission of brominated halocarbons. Measurements ofbrominated halocarbons in this region are sparse, and despitethe new measurements reported here, the region remains datapoor.

Acknowledgements.We would like to thank MOSTI (MalaysianMinistry of Science, Technology and Innovation). for givingopportunities and financial support for the University of Malaya(UM) and Universiti Kebangsaan Malaysia to participate in thisscientific cruise, and other Malaysian public universities andagencies who helped during sampling. The Malaysian RoyalNavy is thanked for their help and assistance in all aspects of thecruise. We also thank the SHIVA European FP7 project (grant226224), NERC, NERC-NCAS and the British Council, througha PMI2 grant, for their support. Neil Harris would like to thankNERC for his Research Fellowship; Emma Leedham and MattAshfold thank NERC for studentships, and Doreena Dominick,

Lin Chin Yik, Fatimah Ahamad and Nur Ily Hamizah for theirassistance and the Ministry of Higher Education Malaysia (KPT’s)ERGS grant ER025-2013A. Finally, we also would like to thankUniversiti Kebangsaan Malaysia (UKM) for the ICONIC-2013-004grant, MOSTI e-science grant 04-01-02-SF-0752 for UniversitiKebangsaan Malaysia (UKM), UKM GGPM-2013-080 and UKMDPP-2014-162 and GUP-2013-057 for financial support.

Edited by: R. Sander

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http://dx.doi.org/10.5194/bg-10-3615-2013

http://dx.doi.org/10.5194/bg-10-3615-2013




http://dx.doi.org/10.1029/2004GL020597

http://dx.doi.org/10.5194/acpd-14-4957-2014

http://dx.doi.org/10.1038/439275a

http://dx.doi.org/10.1007/s10811-013-9990-x

http://dx.doi.org/10.1029/2006JD007264

http://dx.doi.org/10.5194/acpd-14-9729-2014

http://dx.doi.org/10.1029/2005JD006303

bromocarbons in the tropical coastal and open ocean ... · 8138 m. s. mohd nadzir et al.:...

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