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Heavy metals in edible seaweeds commercialised for human consumption

Heavy metals in edible seaweeds commercialised for human consumption

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Heavy metals in edible seaweeds commercialised for human consumption
Victoria Besada
, José Manuel Andrade
, Fernando Schultze
, Juan José González
Centro Oceanográ
co de Vigo, Instituto Español de Oceanografía, Apdo. 1552, 36200 Vigo, Spain
Departamento de Química Analítica, Universidad de A Coruña, Campus da Zapateira s/n 15071, A Coruña, Spain
a r t i c l e i n f o a b s t r a c t
 Article history:
Received 28 September 2007Received in revised form 14 October 2008Accepted 21 October 2008Available online 29 October 2008
Though seaweed consumption is growing steadily across Europe, relatively few studies havereported on the quantities of heavy metals they contain and/or their potential effects on thepopulation's health. This study focuses on the
rst topic and analyses the concentrations of sixtypical heavy metals (Cd, Pb, Hg, Cu, Zn, total As and inorganic As) in 52 samples from 11 algae-based products commercialised in Spain for direct human consumption (
Himanthalia elongata
Hizikia fusiforme
Ulva rigida
Chondrus crispus
Porphyra umbilicales
Undaria pinnati
edbyatomicabsorptionspectrometry(CuandZn by
ame AAS; Cd, Pb and total As by electrothermal AAS; total mercury by the cold vapourtechnique; and inorganic As by
ame-hydride generation). Accuracy was assessed byparticipation in periodic QUASIMEME (Quality Assurance of Information in MarineEnvironmental Monitoring in Europe) and IAEA (International Atomic Energy Agency)intercalibration exercises. To detect any objective differences existing between the seaweeds'metal concentrations, univariate and multivariate studies (principal component analysis,cluster analysis and linear discriminant analysis) were performed. It is concluded that the
Hizikia fusiforme
samples contained the highest values of total and inorganic As and thatmostCdconcentrationsexceededtheFrenchLegislation.Thetwoharvestingareas(AtlanticandPaci
c oceans) were differentiated using both univariate studies (for Cu, total As, Hg and Zn)and a multivariate discriminant function (which includes Zn, Cu and Pb).© 2008 Elsevier B.V. All rights reserved.
Marine algaeEdible seaweedHeavy metalsSpainPattern recognition
1. Introduction
Asian cultures have traditionally employed seaweeds(macroalgae) as a natural source of food and medicines, and Japan, Korea, China, Vietnam, Indonesia and Taiwan arebyfarthe largest consumers (FAO, 2002). Six million tons of freshalgae are now cultivated per year worldwide, amounting toaround 90% of the commercial demand (FAO, 2002).In addition to the general use of algae extracts as additivesand intermediate food products, direct consumption has beensteadily growing since the early 1980s (Hou and Yan, 1998),particularly in western countries, which had formerly beenreluctant to eat seaweed. Consumers in most developedcountries are turning to more natural and nutritional productssuch as seaweed-based products, many of which have unri-valledhealthyproperties(Nettenetal.,2000).Itisnowpossibleto
nd out a large variety of products derived from macro andmicroalgaethroughout Spain and a huge increase in consump-tionisexpectedinthenextfewyears(Ortega-Calvoetal.,1993).Seaweedsareharvestedandcultivatedinwesterncountriesmostly to extract agar, carrageenans and alginates (known ashydrocolloids or phycocolloids) (Radmer, 1996). Hydrocolloidshaveattainedcommercialsigni
cancebecausetheyareusedinvarious industries, particularly food production. However,many seaweeds are consumed directly after only minor pre-processing (mostly drying). Red algae (mainly,
,commercial name
) are consumed frequently since they
 Journal of Marine Systems 75 (2009) 305
Corresponding author. Tel.: +34 986492111; fax: +34 986498626.
E-mail addresses:
Tel.: +34 981167000; fax: +34 981167065.
Tel.: +34 986492111; fax: +34 986498626.0924-7963/$
see front matter © 2008 Elsevier B.V. All rights reserved.doi:10.1016/j.jmarsys.2008.10.010
Contents lists available atScienceDirect
 Journal of Marine Systems
 journal homepage: www.elsevier.com/locate/jmarsys
are rich inproteins and vitamins B and C. Among brown algae,
,withmorethan12 species),
(generic name
) and
Hizikia fusiforme
(generic name
) are the most consumed.Unfortunately, some seaweeds exhibit a high af 
nity forheavymetals(BryanandHummerstone,1973)and,indeed,theyhave been usedas biomonitors for metalpollution in estuarineand coastal waters worldwide and to evaluate the quality of their surrounding environment (Chmielewská and Medved,2001; Topcuoglu et al., 2001; Villares et al., 2005; Melville andPulkownik, 2006). However, heavy metal concentrations inalgaearestronglydependentontheenvironmentalparametersof the sampling sites (salinity, temperature, pH, light, nutrientconcentrations,oxygen,etc)(Zbikowskietal.,2006)andonthestructural differences among the algae (Favero et al.,1996).We have foundfewstudies of thelife-cycle of the seaweedsconsidered in this study, their physiological behaviour, theirelement accumulation patterns, and how the geochemicalprocessesinvolvedintheuptakeofdifferentelementsaffecttheaccumulation of particular metals. Without doubt, there are agreatdealofresearchopportunitiesinthese
elds(Brownetal.,1999). Furthermore, these parameters are strongly dependenton the particular seaweed, so extrapolations cannot be madefrom other species. Nevertheless, some general ideas can begiven in this introductory section and more speci
c commentsare included in theResults and discussionsection.The capacity of algae to accumulate metals depends on avariety of factors, the two most relevant ones being thebioavailability of metals in the surrounding water and theuptake capacity of the algae (Sanchez-Rodriguez et al., 2001).Uptake is currently considered to take place in two ways. The
rst is a surface reaction inwhich metals are absorbed by algalsurfaces through electrostatic attraction to negativessites. Thisis independent of factors in
uencing metabolism such astemperature, light, pH or age of the plant, but it is in
uencedbytherelativeabundanceofelementsinthesurroundingwater.ThisseemstobethemainuptakemechanismforZn.Thesecondis a slower active uptake in which metal ions are transportedacross the cell membrane into the cytoplasm. This form of uptake is more dependent upon metabolic processes (it seemstobetherelevantoneforCu,Mn,SeandNi),anditissubjecttovariations due to changes in temperature, light, or age of theplant (Sanchez-Rodriguez et al., 2001).Itisalsoworthnotingthatphysiologicalchangesandgrowthcan affect concentrations of metals in the macroalgal tissue(Huerta-Diaz et al., 2007). The concentrations are generally lowin summer when growth rates are high and the accumulatedmetals are diluted, and high in winter when the metabolicprocessesslowdown(BrixandLyngby,1983;HouandYan,1998;Villares et al., 2002, cited inZbikowski et al., 2006). The concentrations of Mn, Cu, Zn and Ni may be controlledby enzyme cofactors, and concentrations of Zn may also becontrolled by activators of dehydrogenases and protein-synth-esisenzymes.Fe,CuandZnmayalsoaccumulateinalgaltissue(Lobban and Harrison,1994, cited inHuerta-Diaz et al., 2007). Furthermore, the mobilisation of metals from the sediment inareascoveredbylargeamountsofmacroalgaecouldcontributetotheiraccumulation.Somespeciesareabletoabsorbelementsdirectly from sediment (through the roots, in which metalconcentrations are much higher than in the water column)(Zbikowski et al., 2006).Oneoftheseaweedsconsideredinthepresentstudy,Ulva,isan opportunistic alga that grows quickly under favourableconditions, and this maycause rapid dilution of elements in itstissues (Villares et al., 2005). However, seasonal
uctuations inmetal concentrations in
Ulva rigida
have been attributed togrowth, age of tissue and abiotic factors (salinityand tempera-ture), as well as to variations in metal concentrations in theenvironment(Villaresetal.,2002).Also,becauseof thelaminarstructure of 
Ulva lactuca
(with a relatively high surface area), itmainly takes up solubilised metals (Villares et al., 2001).Ingeneral, greenalgae have alowermetal-bindingcapacitythanbrownalgae(SchiewerandWong,1999)andthelatterareapparentlyunabletoregulatetheuptakeoftraceelements dueto the presence in their cell walls of a large number of compounds (e.g. alginic acid and proteins).Surprisingly, there is little legislation on seaweeds in theEuropean Union, so little control is exercised on potentiallyharmfulmetals.Francewasthe
rstEuropeancountrytosetupregulations on the use of seaweeds for human consumption asnon-traditional foods. Currently 12 macroalgae and 2 micro-algae are authorised as vegetables and dressings/
0.1mg/kgd.w.; and inorganic As
3 mg/kg d.w.At present, neither Spain nor the European Union (EU) hasspeci
clegislationonthissubject.TheEURegulationforPb,Cdand Hg in foodstuffs (European Commission, 2006) does notconsider algae, and efforts are currently being made by aCommittee of Experts within the European Commission, the
Industrial Contaminants
working group, to decide whethergeneraladviceoraspecialregulationshouldbeissued.TheonlySpanishlegislationconcernsseaweedsforanimalconsumptionand states that inorganic As should be less than 2 mg/kg d.w.and that special care should be devoted to
Hizikia fusiforme
(BOE, 2004). A very recent paper (Nakajima et al., 2006) also demonstrated that Hiziki ingestion can be considered equiva-lent to As(III) intake from polluted water as the urinary arseniclevel of volunteers was close to that of individuals withhyperkeratosis and hyperpigmentation in regions endemic forarsenic poisoning; accordingly, long-term ingestion of Hizikimight cause arsenic poising.To the best of our knowledge only a very small number of papers analysing heavy metals in edible algae have beenpublished (they will be referred to hereinafter), and this iscurrentlyanemerging
eld.Thereisalsoaneedtocomparethemetalcontentinalgaefromdifferentproductionareas.Theaimof this work is therefore to provide information on theconcentrations of several harmful heavy metals present incommercialised seaweed samples. This may contribute tocurrentdiscussionsonissuingjointqualitycontrolsonseaweedquality within the European Union and help to determinewhetherseaweedscanbedifferentiatedobjectivelybyemploy-ing chemical measurements.
2. Materials and methods
 2.1. Samples
Samples were obtained from specialist shops throughoutSpain.Mostofthemcontainedonlyonetypeofseaweedthoughsomeweremixturesofdifferentalgae(termed
V. Besada et al. / Journal of Marine Systems 75 (2009) 305
samples of a unique seaweed were provided by a Spanish
rmspecialised in growing/harvesting and marketing seaweed.Efforts were made to acquire as many different samples(
) aspossiblefromboth theAtlanticand Paci
c Oceansand cover most commercially available options. In addition,someagarsampleswereincludedinthisstudybecauseoftheirwidespread use in foods (e.g. as thickening agents in meatproducts and desserts).In total, 52 seaweed samples were analysed in this study:agar (
); arame (
Eisenia bicyclis
); seaweedspaghetti (
Himanthalia elongata
); hiziki (
Hizikia fusiforme
);kombu (
spp); sea lettuce (
Ulva rigida
); Irish moss
(Chondrus crispus
); nori (
Porphyra umbilicales
) and wakame(
Undaria pinnati
). In addition, two seaweed
werefound, one composed of a mixture of wakame, ogonori,kombu, agar and akamodoki (algae salad number 10) andthe other of wakame, nori and sea lettuce (seaweed saladnumber11).Allsamplesweredried,groundandhomogenisedin the laboratory prior to analysis.
 2.2. Analytical measurements
ttedtoastainlesssteelcontainer(measure-mentofinorganicAsrequiredonly0.5g).Afteradditionof1mL ofultrapurewater(Milli-Q,Millipore)and6mLofconcentratednitricacid(Merck,Suprapur),thereactorwassetto90°Cfor2handthen to 130°C for 4 h. Thedigested samplewas transferredto avolumetric
ask and made up to 25 mL with Milli-Q water.Quanti
cation was performed using a Perkin-Elmer AAna-lyst 800 spectrophotometer, equipped with a Zeeman back-ground correction device (Cu and Zn by
ame AAS; Cd, Pb andtotal As by electrothermal AAS). The operational parametersand matrix modi
ers were those recommended by themanufacturer. Total Hg was determined by the cold vapourtechnique, employing a Perkin-Elmer FIMS-400 system (SnCl
as reducing agent). Determination of inorganic As includedsolubilisationwithhydrochloricacid,reductionandsubsequentextractionwithchloroform,back-extractionintodilutedhydro-chloric acid, dry-ashing, and quanti
cation by hydride genera-tion AAS employing a Perkin-Elmer FIAS 200 device (Muñozet al., 1999a). The detection limits expressed in mg/kg dryweight were Pb: 0.008; Cd: 0.005; Hg: 0.001; Cu: 0.2; Zn: 1;total As: 0.050; and inorganic As: 0.020.All analytical protocols were included in a quality controlsystem,whichincludedanalysisofcerti
edreferencematerials,duplicated samples, procedural blanks and international inter-laboratory exercises such as those from QUASIMEME and IAEAon a regular basis (Wyse et al., 2003; Quasimeme, 2004).Table 1shows the analytical results (mean±SD) for eightindependent analyses of two certi
ed reference materials: asea lettuce,
Ulva lactuca
(CRM 279) and an aquatic plant,
La- garosiphon major 
(CRM 60), both from the EU CommunityBureau of Reference. It is seen that the results agreed with thecerti
ed ones.Duetotheabsenceofcerti
ed(orguide)valuesforinorganicAs in the CRMs available for different organic matrices, a seaorganism (the dog
sh muscle,
Squalus acanthias
, NationalResearch Council of Canada, DORM-2 CRM) was selected to
the protocol for measuring inorganic As. This CRMhadpreviouslybeenanalysedbyMuñozetal.(1999a,b),alsoforinorganicAsandwiththesamemethodologyasthatemployedhere. These authors worked with samples whose inorganic Ascontents were in thesamerange astheseaweedsstudied here.These were therefore the only published data we could
nd toevaluate the trueness of the analytical methodology. Ourresults,0.136±0.007mg/kgd.w.(mean±SDforsixindependentanalyses),agreedwiththoseof Muñozetal.(1999b),i.e.0.145±0.011mg/kgd.w.,andthissupportedasatisfactoryperformanceof the method. In addition, in recovery studies carried out byspiking aliquots of the reference materials, the averagerecoveries were: 98.9% for Cd , 99.6% for Pb, 105.1% for Hg,102.4% for Cu, 98.2% for Zn and 104.2% for total As (using theCRM279). For CRM60,the values were: 104.1%,101.4%,108.8%,97.5%, 106.4% and 97.1% for Cd, Pb, Hg, Cu, Zn and total As,respectively. Recovery for inorganic As was 93.8%.
 2.3. Statistical analysis
All studies were performed using Statgraphics v5Plus andSPSS v11; all tests were performed at a 95% con
dence level,unless otherwise stated.
3. Results and discussion
TheexperimentalconcentrationsaresummarisedinTable2.Although the determination of inorganic elements in variousalgae in different countries has been summarised elsewhere(Hou and Yan, 1998), it is dif 
cult to compare results fromvarious authors because of differences in sample treatmentsand analytical procedures. Furthermore, several studies attrib-utedseasonalvariationsinthemetalconcentrationstothealgalgrowth rate. For instance, concentrations decreased in macro-algae during growing periods and increased during the winterdormant period (Phillips,1994), the possible causes for whichincluded allometric parameters (in
uencing metal uptake andaccumulation), environmental factors (affecting metal accu-mulation,Brown et al., 1999), and local variation in salinity(affecting biological uptake,Netten et al., 2000).Here, a preliminary univariate study was performed con-sidering all samples and elements. Then, multivariate studiesaddressed whether the heavy metals studied differentiateseaweeds according to their type and/or geographical origin.
 3.1. Univariate studies 3.1.1. Cadmium
 Table 1
Comparison between experimental results and certi
ed values for two CRMs(mg/kg dry weight)Element CRM 279 CRM 60Certi
ed Measured Certi
ed MeasuredCadmium 0.274±0.022 0.271±0.017 2.20±0.10 2.29±0.17Lead 13.40.36 13.42.15 63.3.2 64.4.6Mercury 0.041
0.049±0.016 0.34±0.04 0.37±0.04Copper 13.14±0.37 13.46±0.78 51.2±1.9 49.9±2.9Zinc 51.3±1.2 50.4±2.5 313±8 333±7Total Arsenic 3.09±0.20 3.22±0.81 8
Indicative value.307
V. Besada et al. / Journal of Marine Systems 75 (2009) 305

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