Mineral elements in milk and dairy products · Š. ZAMBERLIN et al.: Mineral elements in milk and dairy products, Mljekarstvo 62 (2), 111-125 113 between the cytoplasm of blood cells

Š. ZAMBERLIN et al.: Mineral elements in milk and dairy products, Mljekarstvo 62 (2), 111-125 111

Introduction

Onaverage,mineralelementsaccountfor4%oftotalbodymassandpartofeverytissue, liquid,cellandorganinhumanbody.Thereisasufficientevidence that minerals, both independently or inproperbalancewithotherminerals,havestructural,biochemicalandnutritionalfunctionsthatareveryimportant for overall human health, both mentaland physical (Vahčić et al., 2010). Furthermore,theyactascatalystsformanybiologicalreactionsinthebody,includingmusclecontraction,transmissionofnerve impulsesandutilizationofnutrientsfromfood (Anonymous, 2010; Vahčić et al., 2010).Twentymineralelementsareassumedtobeessen-tialinhumannutrition:sodium,potassium,chloride,calcium, manganese, selenium, iodine, chromium,cobalt,molybdenum,fluorine,arsenic,nickel,siliconand boron (Cashman, 2002a). Essential mineralsareoccasionallyclassifiedintotwogroups:majorele-ments(macrominerals)andtraceelements(ormicro-minerals).Theconcentrationofmajorelements(so-dium,potassium,chloride,calcium,magnesiumandphosphorus)inthehumanbodyexceeds0.01%ofto-

*Corresponding author/Dopisni autor: E-mail: [email protected]

Preglednirad-Review UDK:637.046

Mineral elements in milk and dairy

products

Šimun Zamberlin*, Neven Antunac, Jasmina Havranek, Dubravka Samaržija

UniversityofZagreb,FacultyofAgriculture,DepartmentofDairyScience,Svetošimunska25,10000Zagreb,Croatia

Received-Prispjelo:21.02.2012.Accepted-Prihvaćeno:24.05.2012.

Summary

Mineralelementsoccurinmilkanddairyproductsasinorganicionsandsalts,aswellaspartoforganicmolecules,suchasproteins,fats,carbohydratesandnucleicacids.Thechemicalformofmineralelementsisimportantbecauseitdeterminestheirabsorptionintheintestineandtheirbio-logicalutilization.Themineralcompositionofmilkisnotconstantbecauseitdependsonlactationphase,nutritionalstatusoftheanimal,andenvironmentalandgeneticfactors.Theobjectiveofthisresearchistopointouttheresearchresultsofchemicalform,contentandnutritionalimportanceofindividualmineralelementsthatarepresentinvariousmilksanddairyproducts. Key words:milk,dairyproducts,mineralelements,nutritionalsignificance

talbodymass,whereastraceelements(remaining14elements)arepresentinmuchlowerconcentrations,andtheirdietaryintakemaybelowerthan100mg/day.Allessentialmineralelementscanbefoundinmilkbecausebydefinitionitcontainsthenutrientsrequiredforgrowthoftheyoung(BatesandPren-tice,1996).Milkanddairyproductsareanimpor-tant source of dietaryminerals inmany Europeancountries, accounting for 10-20% of daily dietaryintake.However,thecontentofmajorandtraceele-ments inmilk depends upon the content of theseelements in soil andcattle feed,whichvariescon-siderablyamongandwithincountries(Dobrzańskiet.al.,2005;Malbeetal.,2010).Also,thethermaltreatment of milk may have influence onmineralcompositioninthewaythatconcentrationofdietarymineralsinconsumermilkislowerthanconcentra-tioninrawmilk,withtheexceptionofiron,whichishigherinconsumermilk(Malbeetal.,2010).Ontheotherhand,inthestudyconductedbyZurera-Cosanoetal. (1994)theexistenceof statisticallysignificantdifferenceswereobservedonlyforcop-per and iron with a tendency to decrease slightly

112 Š. ZAMBERLIN et al.: Mineral elements in milk and dairy products, Mljekarstvo 62 (2), 111-125 (2012)

duringpasteurizationandsterilization.Inmilk,min-eral elements occur in several chemical forms, in-cludinginorganicionsandsalts,oraspartsoforganicmoleculessuchasproteins,fats,carbohydratesandnucleicacids.

Theobjectiveofthisresearchistopresenttheresearch results that have been conducted on thechemicalforms,contentandnutritionalimportanceofindividualmineralelementsfoundinvarioustypesofmilkanddairyproducts.However, it shouldbeemphasizedthatthereareinsufficientresearchesonthecontentandchemicalformofminerals inmilkanddairyproducts.

Chemical form and distribution of mineral ele-ments in the soluble and colloidal milk phase

Thechemicalformofmineralelementsfoundinmilkanddairyproductsisveryimportantduetotheirabsorptionintheintestineandbiologicalutili-zation(transport,assimilationincellsandconversionintobiologicallyactiveform).Ofthetotalcalciumincowmilk,99%ispresentintheskimmilkfrac-tion.Two-thirdsofthetotalcalciumcanbefoundascalciumphosphateinthecolloidalphasee.g.caseinmicellesorascalciumionsboundtophosphoserine(approximatelyone-sixthoftotalcalcium).There-mainingone-ofcalciuminmilkcanbefoundinthesolublephase.Ioniccalciuminthesolublephaseac-countsforapproximately10%oftotalcalciumandtheremainingpartofsolublecalciumascalciumci-trate.Inaddition,asmallquantityofcalcium(0.15%) is bound toα-lactalbumin (Cashman,2002a).Ofthetotalphosphorusfoundincowmilk,20%oc-cursasorganicphosphateboundtocasein,and80%asinorganicphosphate.Ofthetotalcontentofinor-ganicphosphate,44%isboundtocaseinmicellesascalciumphosphateand56%ispresentinthesolublephase,mostlyasfreephosphateions.Incowmilk,98-100%ofmagnesiumisfoundintheskimmilkfraction,65%ofwhichinthesolublephase(40%asmagnesiumcitrate,7%asmagnesium-phosphateand16%asfreeions).Theremainingpartinthecol-loidalphaseisboundtocaseinmicelles(50%tocol-loidalcalciumphosphateand50%tophosphoserineincasein).Thebalanceofsaltsbetweenthesolubleandthecolloidalphaseincow,goatandsheepmilkis important for definition of their inherent nutri-tionalproperties.Also,thebalanceisimportantfor

maintainingmineralelementsincheesecurdduringcheeseproduction(Cashman,2002a).Insamplesofgoatmilk,takenfromdifferentherdsinthemid-dleof lactation,thecontentofcalcium,magnesiumandphosphorusinthesolublephasewas33%,66%and39%,respectively(Fuenteetal.,1997).Also,research results of themineral elements content inEuropeangoatbreedsshowthatthecontentofsolu-blecalciumrangesfrom30%to38%(O’ConnorandFox,1977;Remeuf,1993).Furthermore, re-search shows that the contents of magnesium andphosphorus in the soluble phase of goat milk are66%and39%, respectively,while thecontentsofcalcium,magnesium and phosphorus in sheepmilkin the soluble phase amounts to 21 %, 56 % and35%(Pellegrinietal.,1994).Mostzincingoatandsheepmilk(93%insheepand89%ingoatmilk)andmanganese(93%insheepand89%ingoatmilk)ispresentinthecolloidalphase(Fuenteetal.,1997).Thedistributionofironandcopperbetweenthetwophasesofgoatandsheepmilkshowsgreaterdiffer-ences thanother researchedmineralelements.Forexample, the solublephaseof sheepmilkcontains29%ironandgoatmilk44%.Incomparison,sheepmilkcontainsahigherlevelofsolublecopper(33%)thangoatmilk(18%)(Fuenteetal.,1997).

Concentration of major mineral elements in various milk types and dairy products

Theaverageconcentrationofmajorelementsingoatandsheepmilkishigherinrelationtocowmilk(exceptsodium),andseveraltimeshigherinrelationtohumanmilk(Table1).Theconcentrationofma-jorelementsdependsonthespecies,theindividualanimal,themethodoffeeding,lactationstage,andhealthconditionoftheudders(ParkandChukwu,1988;Cashman,2006).

MaravalandVignon(1982)observedsignifi-cant changes in the concentration of mineral ele-mentsingoatmilkinthefirst7weeksoflactation.Furthermore,Khanetal.(2006)foundsignificantinfluenceofseasonandbreedontheconcentrationofmostmineralelements in sheepmilk.Thecon-tentofmajorelements inmilkdiffers significantlyfromthecontentinblood.Comparedtoblood,milkcontainsmorepotassium,calciumandphosphorus,andlesssodiumandchloride.Thisisduetothesodi-um-potassiumpumpthatregulatesosmoticpressure


betweenthecytoplasmofbloodcellsandmilk.Atthesametime,calciumistransportedfromtheba-salmembranetocytosolandonwardintotheGolgiapparatusofthealveolarcellsofthemammaryglandstobeincorporatedintocaseinmicelles(PaulinaandBencini,2004).Thetransportofions,lactoseandwateramongblood,intercellularalveolarliquidsandmilkisveryimportantforosmoticbalanceinhealthyudder,and itshowsapositivecorrelationwiththequantityofmilkproduced(PaulinaandBencini,2004).Thereisaveryhighinverselevelofcorrela-tion between the lactose content and the concen-trationof sodiumandpotassium ingoatandothermilktypes(Konaretal.,1971;ParkandChukwu,1988).Particularlyhighlevelofsodiumwasdeter-minedincowcolostrum.However,thesodiumcon-centrationinmilkdecreasestoaveragelevelsafewdays later. Sodium concentration inmilk does notdependonitsdietaryintake.Itishigherattheendofthelactationperiod,whenthequantityofmilkisreduced.Also,milkskimminghasnoeffectonthesodium content (Cashman, 2002a).Unlike othermineral elements, the potassium concentration in

cowcolostrumislowerthaninmilk,butitincreasesoverthenexttwotothreedaysofthelactationperioduntilanormalvalueisreached.Itdependsondietarypotassiumintake.Researchresultshaveshownthatchlorideconcentrationisinpositivecorrelationwithpotassium concentration and negative correlationwith lactosecontent.Thepotassiumconcentrationingoatmilkdoesnotdependonthelactationphase(Konaretal.,1971).Thechlorideconcentrationincolostrum is increased.However, it decreases to anormallevelwithintwotothreedays.Towardsendoflactation,chlorideconcentrationincreasesnotde-pendingonfoodintake.Ingeneral,asfatcontentinmilkincreases,thecontentofthemajormineralsinmilkanddairyproductsdecreases.

Ofthe20essentialmineralelements,calciumisthemostcommoninmilk(Table1).Thecalciumcon-centrationofcowmilkisslightlyhigherincolostrumandat theendof the lactation.Removing fat frommilkdoesnotaffectthemagnesiumcontent.Itscon-tentistwotothreetimeshigherincolostrumthaninmilk,butdecreasesfromthefirsttothethirddayoflactationtoreachitsnormallevel(Table1).

Table1.Concentrationrangesofmajormineralelementsingoat,sheepandcowmilkcomparedtohumanmilk(Posati andOrr,1976;Jenness,1980;Park andChukwu,1988;Park andChukwu,1989;Conietal.,1999;Park,2006;DeutchenForschungsanstaltfürLebensmittelchemie,2012)

Mineralelement

Milk

Goat Sheep Cow Human

Calcium(mg/100g) 106-192 136-200 107-133 22-41

Phosphorus(mg/100g) 92-148 80-145 63-102 12-17

Magnesium(mg/100g) 10-21 8-19 9-16 3.0-3.4

Potassium(mg/100g) 135-235 174-190 144-178 46-55

Sodium(mg/100g) 34-50 29-31 40-58 12-15

Chloride(mg/100g) 100-198 71-92 90-106 32-49

Table2.Averagecontentofmajormineralelements indriedandconcentratedmilk incomparisonwithpasteurizedskimmedmilk(mg/100g)(Hollandetal.,1995)

Mineralelement

Milk

Pasteurized

skimmed

Dried

skimmedEvaporated Condensed

Sodium 55 550 180 150Potassium 150 1590 360 450Chloride 100 1070 250 300Calcium 120 1280 290 330Phosphorus 95 970 260 270Magnesium 12 130 29 33


Themagnesiumcontentinmilkisnotdepend-ing on its dietary intake (Cashman, 2002a). Thecontentof calcium,phosphorus andmagnesium indairyproductsisshowninTables2to5.Ingeneral,thehighestquantitiesofcalciumandphosphorusarefound in hard cheeses (Parmigiano,Gouda, EdamandCheddar - a level up to 10 times higher thaninmilk).Thelowestcontentoftheseelementswasrecorded increamandcottagecheese.Magnesiumcontent in cheese changes in the sameway as thecalciumcontent(Table5).

Nutritional importance of major mineral elements present in milk and dairy products

The recommended daily allowance (RDA) ofsomemajor elements is shown in Tables 6 and 7.RDA values present the average daily calorie andnutrientintakethatisconsideredsufficienttomeettheneedsofhealthyinfants,childrenandadults.

Sodium is themajor cation in the extracellu-lar fluids and is an important regulator of osmoticpressure, acid-basebalance and cellularmembranepotential.Itisalsoimportantfortheactivetranspor-tationofsubstancesthroughthecellularmembrane.The contribution of cowmilk to daily sodium in-takeinhumannutritionislow,butcheeseandsomecreamproductswhich contain addedquantities ofsalt,canprovidesignificantsourcesofsodium.

Chloride is the most important extracellularanion. It is responsible formaintaining electrolytebalance.Excessiveintakeoftablesalt(sodiumchlo-ride) increases urinary calcium excretion, whichnegatively affects bone condition (Massey andWhiting,1996;CashmanandFlynn,2003).TheRDAofchlorideisshownintheTable7.

Potassium isoneof themost important intra-cellularcations.Itoccurs incells inconcentrations30timesgreaterthaninextracellularfluids.Extra-cellular potassium is important for the transmis-sionofnerveimpulses,musclecontractionsandthemaintenance of blood pressure. In addition, it hasbeendeterminedthatpotassiumintakehasaposi-tiveeffectonhumanbones.Forexample,theintakeofalkalinepotassiumsalts(potassiumbicarbonate)by healthy adults significantly reduces urinary cal-ciumexcretion,evenwithexcessivetablesaltintake(Morrisetal.,1999).AnadequatedailypotassiumintakeforpeopleisshowninTable7.Thecontentofsodium,potassiumandchlorideinmilkhasaphysi-ologicalsignificanceininfantnutrition.Conversely,excessive intake of these three mineral elementsmaycauseclinicalproblemsbecausetheycanstartaccumulating, limitingtherenalcapacityof infants(Cashman,2002a).

Calciumaccountsfor1.5-2%ofthetotalbodymassofanadult.Ofthisamount,99%isfoundinbones and teeth as calciumphosphate and the re-maining1%inextracellularfluidsandintracellularstructuresaswellasincellularmembranes.

Calcium is responsible for many regulatoryfunctions, such as normal cardiac rhythmmainte-nance, blood clotting, hormone secretion, musclecontraction and enzyme activation (Cashman,2002a).Milkanddairyproducts(cheeseandyogurt)areveryrichsourceofcalcium(Tables1,3and4).ThemajorityofdietaryCa(70%)comesfromdairyproductsbecauseinmilk,caseinmicellesconstitutethe natural vector of Ca (Canabady-RochelleaandMellemab,2010).TheRDAforcalcium(Ta-ble6)isdifficulttoreachwithoutconsumingmilkand dairy products. In the past, special attention

Table3.Averagecontentofmajormineralelementsinbutter,yogurtanddairyicecream(Hollandetal.,1995)

Mineralelement

Dairyproduct(mg/100g)

Butter Yogurt Icecream

Sodium 750a 80 69

Potassium 15 280 160

Chloride 1150a 170 110

Calcium 15 200 130

Phosphorus 24 170 110

Magnesium 2 19 13

abuttertowhichsaltwasadded.Butterwithoutaddedsaltcontains11mg/100gofsodiumand17mg/100gofchloride


wasdevoted to thebioavailabilityof calciumfrommilk.Theaveragecalciumabsorptionfromcowmilkvariesbetween21%and45%.Also, thebioavail-abilityofcalciumfromcheeseandyogurtequalstothosefrommilk.

CalciumabsorptiondependsonthevitaminDlevelandageofaperson.Atthesametime,ithasbeenproventhatcalciumabsorptioninthestomachis also affected by lactose. Furthermore, the dairyproductscalciumbioavailabilityisbetterthanoftheothersources,suchasvegetables.Thiscouldpartlybe due to their contents in highly phosphorylatedfragments of caseins, named caseinophosphopep-tides(CPPs).Thesepeptidesappearmainlyduringtheelaborationofmilkproductssuchascheeseoryoghurt, under the action on caseins of milk-en-dogenous,milk-clotting and/ormicrobial enzymes.TheymayalsoarisefromαS1-,αS2-andβ-kazeinadi-gestioninthegut(FitzGerald,1998;Dupasetal.,2009).OneuniquefeatureofCPPsistheirabilitytoformCPP-metalioncomplexes,whichwouldpoten-tiallyincreasethebioavailabilityofcalciumandiron,

notablybymaintainingmetals ina soluble form inthedistalsmallintestine(Peresetal.,1999;Dupasetal.,2009).Osteoporosisisaverycommondiseaseinwesterncountriesandmostlyaffectswomen.Oneofitscausesinoldageisinsufficientcalciumintakewhen young. Maximum bone mass is achieved inthethirddecadeoflifebyprovidingsufficientcal-cium intake at young age. It has also been proventhatbonemassisanimportantfactorinosteoporosisprevention (Prentice, 1997; Cashman, 2002a).Despitethedatafromthevariouscalciuminterven-tionstudies,thereisstillconsiderabledebateonthemeaningoftheseeffectsofcalciumonbone(Cash-man,2006).

Phosphorusisamajorelementwithmanyim-portant biological functions in the human body. Itoccursasorganicorinorganicphosphateinallbodytissues and fluids, and is the main component ofmany biological compounds, including lipids, pro-teins, carbohydrates andnucleic acids (Cashman,2002a).

Table4.Averagecontentofmajormineralelementsincream(Hollandetal.,1995)

Mineral

element

(mg/100g)

Cream

Freshcream SourcreamSterilized

cannedUHT

≈10%fat ≈20%fat ≈35-48%fat ≈60%fat ≈20%fat ≈25%fat ≈32%fat

Sodium 49 49 37 18 41 53 33

Potassium 120 120 65 55 110 110 92

Chloride 77 80 51 40 81 78 62

Calcium 99 91 50 37 93 86 66

Phosphorus 82 76 50 40 81 73 57

Magnesium 11 9 6 5 10 10 7

Table5.Averageconcentrationsofmajormineralsinparticularcheesevarieties(mg/100g)(Hollandetal.,1995)

Mineral

Cheese

Brie Cheddar Cream Cottage Edam Feta Gouda Parmigiano Stilton

Sodium 700 670 300 380 1020 1440 910 1090 930

Potassium 100 77 160 89 97 95 91 110 130

Chloride 1060 1030 480 550 1570 2350 1440 1820 1410

Calcium 540 720 98 73 770 360 740 1200 320

Phosphorus 390 490 100 160 530 280 490 810 310

Magnesium 27 25 10 9 39 20 38 45 20


Table6.Recommendeddailyallowancesofcalcium,magnesiumandphosphorus(InstituteofMedicine,2011)

Category Age(years)Mineralelement

Calcium(mg) Magnesium(mg) Phosphorus(mg)

Infants0.0-0.5 200 30 1000.5-1.0 260 75 275

Children1-3 700 80 4604-8 1000 130 500

Males

9-13 1300 240 125014-18 1300 410 125019-30 1000 400 70031-50 1000 420 70051-70 1200 420 700>70 1200 420 700

Females

9-13 1300 240 125014-18 1300 360 125019-30 1000 310 70031-50 1000 320 70051-70 1200 320 700>70 1200 320 700

Pregnancy14-18 1300 400 125019-30 1000 350 70031-50 1000 360 700

Lactation14-18 1300 360 125019-30 1000 310 70031-50 1000 320 700

Table7.Recommendeddailyallowancesofpotassium,sodiumandchloride(InstituteofMedicine,2011)

Category Age(years)Mineralelement

Potassium(g) Sodium(g) Chloride(g)

Infants0.0-0.5 0.4 0.12 0.180.5-1.0 0.7 0.37 0.57

Children1-3 3.0 1.0 1.54-8 3.8 1.2 1.9

Males

9-13 4.5 1.5 2.314-18 4.7 1.5 2.319-30 4.7 1.5 2.331-50 4.7 1.5 2.351-70 4.7 1.3 2.0>70 4.7 1.2 1.8

Females

9-13 4.5 1.5 2.314-18 4.7 1.5 2.319-30 4.7 1.5 2.331-50 4.7 1.5 2.351-70 4.7 1.3 2.0>70 4.7 1.2 1.8

Pregnancy14-18 4.7 1.5 2.319-30 4.7 1.5 2.331-50 4.7 1.5 2.3

Lactation14-18 5.1 1.5 2.319-30 5.1 1.5 2.331-50 5.1 1.5 2.3


Ascalciumphosphate,phosphorusisthemostimportantstructuralcomponentofbonesandteeth.However,excessiveintakeofphosphoruscombinedwithreducedcalciumintakemayhavenegativeef-fectsonbones(Cashman,2006).TheRDAofphos-phorusisshowninTable6.Milkanddairyproductsarerichsourceofphosphorusandinwesterncoun-tries account for 30-45%of the total phosphorusintake(InstituteofMedicine,2004).

Magnesium plays an important role in manyphysiologicalprocesses,suchasmetabolismofpro-teinsandnucleicacids,neuromusculartransmissionand muscle contraction, bone growth and bloodpressureregulation.Magnesiumisalsoaco-factorofmanyenzymes.Ontheotherhand,magnesiumdefi-ciencymayalsocauseosteoporosis(Rude,1998).

Therehasnotbeenmuchresearchonthebio-availabilityofmagnesiumfrommilkforthehumanbodyinhumannutrition.Studiesofmetabolicbal-ance have shown that 16-43 % of magnesium isabsorbedfrominfantformulasbasedoncowmilk,and that lactose facilitates magnesium absorption.Inwesterncountries16-21%oftotalmagnesiumisconsumedthroughmilkanddairyproducts(Cash-man,2002a).

Concentration of trace elements in milk and dairy products

Unlikethemajorelements,traceelementsarepresent in the human body in the concentrationslower than0.01%of the totalbodymass.Of the20 essentialminerals, 14 are trace elements: iron,copper,zinc,manganese,selenium,iodine,chromi-um, cobalt,molybdenum, fluorine, arsenic, nickel,siliconandboron.Scientificresearchesontestani-malshaveproventhatsomeoftheaboveelements(arsenic, nickel, silicon and boron) are essential.Therefore,itisassumedthattheyarealsoessentialforhumans(Cashman,2002b).Manyothertraceelementsalsooccurinmilk.However,theyarenotnutritionallyimportant.Theseincludelithium,bro-mine,aluminium,strontium,silver, lead, tin,vana-dium,mercury,cadmium,rubidiumandcaesium.

Manyofthetracemineralelementsaretoxic.However, their concentrations inmilk are too lowtopose a threat tohumanhealth. Like contentofothermineralspresentinmilk,theconcentrationoftrace elements (Table 1 and 8) is not constant. Itdependsonthelactationstage,nutritionalstatusofthe animal, and environmental and genetic factors(Cashman,2002b).Thecontentoftraceelements

Table 8.Concentrations of trace elements in goat, sheep and cowmilk compared to humanmilk (Po-sati and Orr, 1976; Jenness, 1980; Park and Chukwu, 1988; Park and Chukwu, 1989;FlynnandCashman,1997;Conietal.,1999;Park,2006;DeutchenForschungsanstaltfürLebensmittelchemie,2012)

MilkMineralelement Goat Sheep Cow HumanSulphur(mg/100g) 28 29 32 14Iron(µg/100g) 36-75 62-100 30-70 26-58Copper(µg/100g) 11 11-88 2-30 22-77Manganese(µg/100g) 5.5 5.3 1.3-4.0 700ngZinc(µg/100g) 242 415 74-145 0.38Iodide(µg/100g) 2.1-11 2.0 2.0-6.0 0.5-9.0Selenium(µg/100g) 0.7 0,9 1.3-1.7 1.0-5.3Fluoride(µg/100g) - - 11-21 13-25Cobalt(ng/100g) 270 360 50-130 114Nickel(µg/100g) 0.3-19 5,4 0.4-6.0 0.4-3.0Molybdenum(µg/100g) - - 2.4-6.0 1.0Boron(µg/100g) - - 19-95 -Bromide(µg/100g) 411-503 - 154-293 100Chromium(µg/100g) 0.5-15 0,32 1.0-4.0 4.1Nitrate(µg/100g) - - 20-1240 -Aluminium(µg/100g) 15 51 46 0.06

-nodata


ingoatandothermilktypesalsodependsonthespe-cies, its individual characteristics, feedingmethod,lactationstage,andhealthconditionofudder(ParkandChukwu,1989).Sheepmilkcontainsapproxi-mately0.9%ash,comparedto0.7% incowmilk(Parketal.,2007).Aconclusionmaybe that thecontentofminerals insheepmilkishigherthanincowmilk,primarilyduetodifferences innutritionand metabolism (Rincon et al., 1994). To date,therehasbeen little researchon traceelements insheepmilk,althoughtheycouldplayan importantroleduetotheirpossiblypositiveinfluenceonhu-manhealth.Bycarryingoutdiscriminatoryanalysisofthemineralcompositionin360samplesofrawmilk,(120samplesofcow,goatandsheep)statisticaldis-tanceandsignificantdifferenceswereestablishedin120samplesofcowmilkcomparedto120samplesofgoatmilk,while in10%ofthecasestherewasacorrespondencebetweenthesamplesofgoatandsheepmilk(Jay,2000).Theseresultsclearlyshowaseparationofelementsintermsofthemilk(Jay,2000;HaenleinandWendorff,2006).

Increased exposure of dairy animals to grow-ing environmental pollution has also increased theneed for more research regarding the content ofheavymetalsinmilk.Heavymetals,suchasleadandplatinum,whichcanbefoundinexhaustgases,canbe absorbedwhen animals graze nearmajor trans-portationroutes(Ikedaetal.,1996;Raghunathetal.,1997).Inaddition,negativeeffectsofleadandcadmiumonhumanhealthweredetected.Traceele-mentslikecopperandzincareessentialandhavearole inmany biological functions (Tripathi et al.,1999).However,ifpresentathigherlevels,theycanhave negative effects on human health (Brewer,2010).Researchresultsshowthattheconsumptionof sheepmilk products in Italy leads to an intakeof 15%of thepermissible content of heavymet-als (Coni et al., 1999).The content of cadmium,whichisalsoaheavymetal,issignificantlyhigherinsheepmilkthanincowmilk,probablyduetodiffer-encesinnutritionandmetabolismbetweentwospe-cies(Conietal.,1999;HaenleinandWendorff,2006;Herwigetal.,2011).

Research on other trace elements shows that,for example, the iron concentration inmilk is re-ducedby35to50%inthefirstthreedaysoflacta-tion;afterthatitremainsataconstantlevel,anditdoesnotdependonnutrition.Furthermore,14%of

thetotalironcontentinmilkcanbefoundinmilkfatboundtothemembraneoffatglobules;24%isboundtocasein(probablytophosphoserine);29%islinkedtowheyproteins,while32%isboundtolowmolecularmasscompounds(Cashman,2002b).Bi-oavailabilityofironfromhumanmilkrangesfrom49to70%,whichissignificantlyhigherthanfromcowmilk(10to34%).Thereisnoclearexplanationforthisdifference.However, itmightbeexplainedbythehighleveloflactoferrin(glycoproteinthatbindsironions)presentinhumanmilk.Anotherpossibleexplanation may be found in the high content oflactose and ascorbate inhumanmilk,which facili-tatesironabsorption,andinlowcontentofproteins,calcium and phosphorus, which inhibit absorption(Cashman,2002b).

The average zinc concentration inmilk is 3.9mg/L (Flynn andCashman, 1997).However, itshouldbenotedthattherearegreatvariationsincon-centration(2.0to6.0mg/L).Zincincowcolostrumisreducedby50%inthefirstthreedaysoflactationafter that further change is negligible.Hard sheepcheeses are rich source of zinc (Samaržija et al.,2005)duetoinherenthighconcentrationinsheep’smilk(Table1).Zinc in nutritionalso increases itscontentinmilk.Inaddition,itwasdeterminedthatadditionofzinctomilkresults inreducedsomaticcellcount(Pechovà etal.,2006).Only1to3%ofzincinmilkisrelatedtothelipidfraction,whiletheremainingpartcanbefoundintheskimmilkfrac-tion.Also,outof the total zinccontentpresent intheskimmilkfraction,95%isboundtophosphoser-inebycaseinmicellesand5%tocitrate.Thebioa-vailabilityofzincinhumanmilkismuchhigherthanincowmilk,becauseinhumanmilkit isboundtoligandsoflowmolecularmass(forexample,citrate),which facilitatesabsorption.Also, thebindingofalargeproportionof zinc to casein in cowmilk (10timeshigherthaninhumanmilk),maycause ittobeblockedwithinthecaseincurdthatisproducedintheabdomen,makingitunavailableforabsorption(PabόnandLönnerdal,2000).Contrary,researchconducted on rats established a high capacity forzincabsorption(85to95%)fromhumanandcowmilk,anddairyinfantformula.Itispossiblethatthelowconcentrationofzincinhumanmilkcontributesto better absorption because it is homeostaticallycontrolled,andsmallquantitiesarebetterabsorbedthanlarge(Cashman,2002b).


Theconcentrationofcopperinmilkisalsore-ducedby50% inthefirst threedaysof lactation,butunlikeironandzinc,additionofcoppertoani-malfeedincreasesitscontentinmilk.Thereislittleinformation on the content of absorbed copper inthehumanbody.Experimentsonratsshowed83%absorptionfromhumanmilk,76%fromcowmilk,and86 to87%fromdairy infant formula (Cash-man,2002b).

Manganesecontentishigherincolostrum(100to160µg/L)thaninmilk(20to50µg/L),reducedbymorethen50%inthefirstthreedaysoflacta-tion.Incowmilk67%ofthemanganeseisboundtocasein,1%toglobularfatmembranes,14%towheyproteins, and18% to lowmolecularweightfraction. Research results show that manganeseabsorption from human milk in healthy adultsamounts to 8.2±2.9 % and is significantly higherthanfromcowmilk(2.4±1.7%),whilemanganeseabsorption fromdairy infant formula amounted to1.7±5.9 %. Nevertheless, the absolute content oftheabsorbedmanganesefromdairy infantformulaandcowmilkwashigherthanfromhumanmilkbe-causeof itshigher inherentconcentration in thosetypesofmilk.Ontheotherhand,studiesconductedon ratsdidnot showany significantdifferences inabsorbedmanganesefromhumanandcowmilkand,alsodairyinfantformula(Cashman,2002b).

Selenium in plants is affected by the contentandavailabilityoftheelementinsoilwhileseleniumcontentofmilkisaffectedbytheseleniumcontentinfeedsanditsavailability(Reykdaletal.,2011).Also, processing of milk can diminish seleniumconcentration (Navarro-Alarcon and Cabrera-

Vique, 2008). Selenium is linked to the enzymeglutathioneperoxidase(12%ofthetotalcontent).Lessthan0.1%oftotalseleniumcontentisboundtofat(Cashman,2002b).

Theiodinecontentdependsontheseasonanddietaryintake;itvariesfrom20to>4000µg/L.Themostofiodineinmilk(80to90%)isfoundinin-organic form; another 5 to 13% is bound to pro-teinsbycovalentbondorweakintermolecularbonds(Cashman,2002b).

Thechemicalformofchromiuminmilkisnotknown, although it mostly occurs in triple bondform.Theaveragecontentofchromiumandcobaltinmilkdependsontheirdietaryintake.

Molybdenumcontentinmilkisboundtoxan-thine oxidase and is dependent on feed. Averagefluorinecontentinmilkis20µg/L(rangingfrom10to140µg/L).Approximately46to64%offluorinecontentinmilkispresentasfreeion,theremainingis bound to proteins (Cashman, 2002b).Little isknownaboutthechemicalformsofcobalt,arsenic,nickel, silicon and boron inmilk. The amounts oftheseelementsinmilkanddairyproductsareshowninTables8to12.

Littleresearchisavailableontheeffectsofthelactationstage,nutritional status,andenvironmen-talandgeneticfactorsonthecontentoftheseele-ments.

Nutritional importance of trace elements present in milk and dairy products

Aswithmajorelements,thebestwaytodeter-minethenutritionalimportanceoftraceelementsis

Table9.Averageconcentrationofsometraceelementsinconcentratedmilk(Hollandetal.,1995)

Traceelement

Milk

Pasteurized

skimmed

Powdered

skimmedEvaporated Condensed

Iron(mg/100g) 0.05 0.27 0.26 0.23

Copper(mg/100g) traces traces 0.02 traces

Zinc(mg/100g) 0.4 4.0 0.9 1.0

Manganese(mg/100g) traces traces traces traces

Selenium(µg/100g) 1.0 11 3.0 3.0

Iodine(µg/100g) 15 150 11 74


tocomparetheircontentinmilkanddairyproducts(Tables8to12)withtherecommendeddailyallow-ance(Table13).

Iron as an essential trace elementparticipatesascatalystinseveralmetabolicreactions.Asacom-ponentofhemoglobin,myoglobin, citochromeandotherproteins, ironplays an important role in thetransport,storageandutilisationofoxygen.Itisalsoaco-factorofmanyenzymes(BatesandPrentice,1996).Milkanddairyproductsarepoorsourceofiron.Irondeficiencyinthehumanbodyisoneofthemostcommonhealthissues,occurringininfantsandchildrenbecauseoffastgrowthandlowdietaryin-take.Thisproblemcanbepreventedbyadditionofirontodairyinfantformulassinceadditionalascor-bate in infant formulas improves iron absorption(Bermejoetal.,2002).

Zincisveryimportantforgrowth,sexualdevel-opment,thehealingofwoundsaswellasnormalfunc-tioningoftheimmunesystemandotherphysiologi-calprocesses.Zincisacomponentofthehormoneinsulin.Itassistsinthefunctioningofseveralotherhormones thatare important for reproductionandsynthesisofDNA,RNAandproteins(Salgueiroetal., 2002). It is also a co-factor ofmany enzymesthat are included in most of metabolic processes.Dairyproductssuchasmilk,cheeseandyoghurtarevery important inhumannutrition, but an insuffi-cientsourceofzinc.Itisestimatedthatinwesterncountriesthecontributionofdairyproductstothetotalzincintakerangesfrom19to31%(Cashman,2002b).

Copper isessentialelement important for theabsorptionofironandascofactorofenzymesinglu-cosemetabolismandsynthesisofhemoglobin,con-nectivetissuesandphospholipids(Solaimanetal.,2001).Copperdeficiencyinthehumanbodyisveryrare,occurringonlyincasesoflong-termstarvation.Milkanddairyproductsareapoorsourceofcopper(DavisandMertz,1987)(Tablica9).

Manganese is a specific enzyme co-factor in-volvedinthesynthesisofmucopolysaccharides,anda non-specific co-factor for many other enzymes.Thereareseveralknownmanganesemetaloenzymeslike arginase, glutamine synthetase, phosphoen-lopyruvatedecarboxilaseandmanganesesuperoxidedismutase (Aschner and Aschner, 1991). Man-ganese can be found in significant quantities in allfoodstuffs.Itsdeficiencyhasnotbeenrecordedasacauseofdisturbanceordisease.Cowmilkisapoorsource ofmanganese. Its contribution to the totalmanganeseintakeinwesterncountriesislow(1to3%).Ofthetotaldietaryintakeofmanganeseonly3 to5%are successfullyabsorbed.The remainingquantitiesareeliminatedfromthebodythroughfae-ces(Auetal.,2008).

Selenium is the main component of the en-zyme glutathione peroxidase, which is present inmanytypesoftissues.IncombinationwithvitaminE, catalase and superoxidedismutase, it acts as anantioxidant (Somer and Ínam, 2000). After die-taryintake,seleniumisconvertedintoorganicform,mostlyasseleno-methionine,whichisthenincorpo-ratedintoproteins(Petreraetal.,2009).Insome

Table10.Averageconcentrationsofsometraceelementsincream(Hollandetal.,1995)

Traceelement

Contentin100gofcream

FreshcreamSourcream

Sterilizedcanned

UHT

≈10%fat ≈20%fat ≈35-48%fat ≈60%fat ≈20%fat ≈25%fat ≈32%fat

Iron(mg) 0.1 0.1 0.2 0.1 0.4 0.8 1.0

Copper(mg) traces traces traces 0,09 traces traces traces

Zinc(mg) 0.3 0.5 0.2 0.2 0.5 1.1 0.4

Manganese(mg) traces traces traces traces traces traces traces

Selenium(µg) traces traces traces traces traces traces traces


areasofChinawithlowseleniumconcentrationsinthesoiltherearemanycasesoftheKeshandiseasecausedbyseleniumdeficiency.

Low selenium concentrations in the humanbodyhavealsobeenobservedinNewZealandandFinland,countrieswithlowseleniumconcentrationsin the soil. TheRDAof selenium is shown in theTable13.

Iodineisanessentialcomponentofthyroidhor-mones that are important for the control of basalmetabolismand reproduction. Iodinedeficiency inthehumanorganismcanresultinenlargementofthethyroid gland.On the other hand, a high concen-trationofdietaryiodinecanleadtoaslowdowninthyroidglandfunction(Reidetal.,2008;Sorigueretal.,2010).Iodineistheonlytraceelementthatisconsideredtobeexcessivelypresentinmilk,dueinpart to the excessiveuseof organic iodide saltsandiodophorfordisinfection.TheRDAfor iodineisshowninTable13.Thecontributionofmilkanddairyproductstototaliodineintakerangesfrom6to7%inGermanyto37%inGreatBritain(Schöneetal.,2009).

Molybdenum is also an essential component ofseveralenzymes,includingxanthineoxidereductase,aldehydeoxidaseandsulphiteoxidase,whereitoc-cursasprostheticgroupofmolybdopterin(Hilleetal.,2010).Itisnotknownwhetherthehumanbodyneedsmolybdenumassuchorasmolybdopterin.

The RDA of molybdenum is shown in Table13.Milkcontributessignificantlytototalmolybde-numintake-asmuchas36%inwesterncountries(Cashman,2002b;Yoshidaetal.,2006.).

It is assumed that chromium is an essentialnutrientinhumannutrition.Lackofchromiumcancauseproblemswithlactosetolerance.CobaltisthecomponentofvitaminB12,whichisitsonlyknownfunction. Fluorine is accumulated in hard tissues,such asbones and teeth, and although it is not anessentialelement,itisconsideredimportantbecauseitpreventstoothdecay.TherearenoRDAsbecauselimiting factorhasnotbeendetermined. Itsnutri-tional function is not yet known. Arsenic, nickel,silicon,andboronareessentialelementsinanimals,soitcanbeassumedthatthisisalsothecasewiththe humanbody (Casey et al., 1995).Thenutri-

Table11.Averagecontentofsometraceelementsinbutter,yogurtanddairyicecream(Hollandetal.,1995)

Traceelement

Contentin100gofproduct

Butter Yoghurt Dairyicecream

Iron(mg) 0.2 0.1 0.1

Copper(mg) 0.03 traces 0.02

Zinc(mg) 0.1 0.7 0.3

Manganese(mg) traces traces traces

Selenium(µg) traces 2.0 1.5

Iodine(µg) 38 63 -

Table12.Averagecontentofsometraceelementsinsomecheesetypes(Hollandetal.,1995)

Traceelement

Contentin100gofcheese

Brie Cheddar Cream Cottage Edam Feta Gouda Parmigiano Stilton

Iron(mg) 0.8 0.3 0.1 0.1 0.4 0.2 0.1 1.1 0.3

Copper(mg) traces 0.03 0.04 0.04 0.05 0.07 traces 0.33 0.18

Zinc(mg) 2.2 2.3 0.5 0.6 2.2 0.9 1.8 5.3 2.5

Manganese(mg) traces traces traces traces traces traces traces 0,1 traces

Selenium(µg) 3.6a 12 1.0 4.0 6.4a 5.0a 8.0a 11 11


tionalfunctionsoftheseelementsarestillunknownandtheirRDAshavenotyetbeendefined.Milkanddairyproductsdonotprovideasignificantcontribu-tiontotheirtotalintake,exceptforchromium(21%)andnickel(11%)(Cashman,2002b).

Conclusion

Althoughthesubjectisveryimportanttherearenomanyrecentlypublishedpaperswhicharedeal-

ingwithmineralsinmilkanddairyproducts.Essen-tialmineralelements,includingsodium,potassium,chloride, calcium, manganese, selenium, iodine,chromium, cobalt, molybdenum, fluorine, arsenic,nickel, silicon andboron, canbe found in allmilktypes and dairy products.They are present in theformofinorganicionsandsalts,orarepartoforgan-icmolecules like proteins, fats, carbohydrates andnucleicacid.Sodium,potassium,chlorideandiodinecanbefoundinmilkandinfantformulasinachemi-

Table13.Recommendeddailyallowancesofparticulartraceelements(InstituteofMedicine,2011)

Traceelements

Category Age(Years)

Iron(mg)

Zinc(mg)

Iodine(µg)

Selenium(µg)

Copper(µg)

Manganese(mg)

Fluoride(mg)

Chromium(µg)

Molybdenum(µg)

Infants0,0-0,5 0.27 2 110 15 200 0.003 0.01 0.2 2

0,5-1,0 11 3 130 20 220 0.6 0.5 5.5 3

Children1-3 7 3 90 20 340 1.2 0.7 11 17

4-8 10 5 90 30 440 1.5 1 15 22

Males

9-13 8 8 120 40 700 1.9 2 25 34

14-18 11 11 150 55 890 2.2 3 35 43

19-30 8 11 150 55 900 2.3 4 35 45

31-50 8 11 150 55 900 2.3 4 35 45

51-70 8 11 150 55 900 2.3 4 30 45

>70 8 11 150 55 900 2.3 4 30 45

Females

9-13 8 8 120 40 700 1.6 2 21 34

14-18 15 9 150 55 890 1.6 3 24 43

19-30 18 8 150 55 900 1.8 3 25 45

31-50 18 8 150 55 900 1.8 3 25 45

51-70 8 8 150 55 900 1.8 3 20 45

>70 8 8 150 55 900 1.8 3 20 45

Pregnancy

14-18 27 12 220 60 1000 2.0 3 29 50

19-30 27 11 220 60 1000 2.0 3 30 50

31-50 27 11 220 60 1000 2.0 3 30 50

Lactation

14-18 10 13 290 70 1300 2.6 3 44 50

19-30 9 12 290 70 1300 2.6 3 45 50

31-50 9 12 290 70 1300 2.6 3 45 50


calformwhichallowsanalmostentireabsorptioninthehumanbody.Thebioavailabilityofcalciumandmagnesiumhasnotyetbeensufficientlyresearched.Amongsheep,goatandcowmilkthebioavailabilityofironandzincfromcowmilkisthehighest,how-ever, significantly lower than in humanmilk.Verylittle information is available on the bioavailabilityofcopper,manganese,selenium,fluorineandothertraceelementspresent inmilkanddairyproducts.However,itisassumedthatlactose,ascorbate,cit-rate,phosphopeptidesandlactoferrinhaveasignifi-cantimpactontheabsorptionofmineralelements.Furthermore,milkdoesnotcontainsubstancessuchasphitatesandpolyphenols,whichstrongly inhibittheabsorptionofmineralsinhumanbody.

Mineralni sastav mlijeka i mliječnih proizvoda

Sažetak

Mineralni elementi se u mlijeku i mliječnimproizvodimanalazeuoblikuanorganskihionaisoli,ilikaodioorganskihmolekulakao što subjelanče-vine,masti,ugljikohidratiinukleinskekiseline.Ke-mijska formaukojoj sumineralni elementiprisut-nijevrlovažnajeronjojovisiapsorpcijauželucuitimenjihovobiološko iskorištenje.Mineralnisastavmlijeka nije konstantan i ovisi o stadiju laktacije,hranidbenom statusu životinje, okolišnim uvjetimai genetskim čimbenicima. Cilj ovog rada je prika-zati dosadašnje rezultate istraživanja koncentracija,kemijske forme i prehrambene važnosti pojedinihmineralnihelemenatakojisuprisutniurazličitimvr-stamamlijekaimliječnihproizvoda.

Ključne riječi:mlijeko,mliječniproizvodi,mineralnielementi,prehrambenavažnost

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Mineral elements in milk and dairy products · Š. ZAMBERLIN et al.: Mineral elements in milk and dairy products, Mljekarstvo 62 (2), 111-125 113 between the cytoplasm of blood cells