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RapidDetection ofFoodAdulterants andContaminants

TheoryandPractice

ShyamNarayanJha

CentralInstituteofPost-HarvestEngineering andTechnology,India

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Notices

Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchandexperiencebroaden ourunderstanding,changesinresearchmethods,professionalpractices,ormedicaltreatmentmaybecome necessary.

Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgeinevaluatingandusing anyinformation,methods,compounds,orexperimentsdescribedherein.Inusingsuchinformationormethods theyshouldbemindfuloftheirownsafetyandthesafetyofothers,includingpartiesforwhomtheyhavea professionalresponsibility.

Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors,assumeany liabilityforanyinjuryand/ordamagetopersonsorpropertyasamatterofproductsliability,negligenceor otherwise,orfromanyuseoroperationofanymethods,products,instructions,orideascontainedinthe materialherein.

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Thisbookis dedicatedtomyGrandFather(baba) whoinculcatedhighvaluesand sanskaras inme.Ialwaysstudiedwithhisinspiration,keepinglanternnearhishead whilesleepingindarknightofmyruralvillage

7.4

Preface

Nowadaysfoodsafetyisofparamountimportanceforconsumers,retailers,aswellasregulatorswho areengagedinenactingfoodlaws.Adulterationofhigh-valuefoodswithlow-valueones,color-and taste-enhancingingredients,andmislabelingarerampant,particularlyinprocessedfoodmarkets. Insecticide/pesticideresidues,heavymetals,toxinsbeyondpermissiblelimits,dangerousbacteria, andsooninfreshaswellasprocessedfoodsarenowfoundinvariouscountries.Thesemostlyare checkedbycollectingsamplesfrommarketsandusingtraditionallaboratory(wetchemistry)methods, whicharetime-consuming,laborious,andexpensive.Testreportsusuallyaremadeavailableseveral daysormonthsaftertesting;bythenmanyarealreadyaffectedbyeatingthoseinfectedfoods.Rapid testingmethodsthatcandetectpossibleadulterants,contaminants,andtoxinsinaveryshorttimeand preferablyatthemarketsiteareurgentlyrequiredandthereforeareincreasinglybeingtriedtheworld over.

Numerousarticlesandresearchpapersthatdealwithapplicationsofvariousrapidandoftennondestructivemethodsoffoodtestingarebeingpublishedeveryyear.Foodstandardsandpermissiblelimits ofvariouscontaminantsandtoxinsare,however,differentindifferentcountries.Theaccuracyofthe methodbeingusedalsovaries,anditisdifficulttohaveknowledgeofallstandardsandpermissible limits,thoughthisknowledgechangestimetotimeforeveryone.Thisbookwasdevelopedafter receivinganoverwhelmingresponsetomyearlierbook, NondestructiveEvaluationofFoodQuality: TheoryandPractice,tofillthegapoffoodsafety,includingonechapteroneachofthetopicoffood safetyandquality,commonadulterantsandcontaminants,standardsandpermissiblelimits,aswellas otherchaptersondifferenttechniquescoveringtheory/basicsinbriefandtheirpracticalapplicationsin termsofafewrecentworksreportedintheliterature.

Thepurposeofthisbookistoprovidebasicknowledgeandinformationtopostgraduatestudents andscientistsinterestedintheupstreamresearchonfoodsafetyaspects.Itisparticularlyusefulto beginners.Italsomaybeusefultoresearchersdirectlyengagedindevelopingfast,reliable,andnondestructivemethodsfortheevaluationoffoodqualityandsafetyaspects,aswellasthefoodindustries andregulatorsindirectlyresponsibletocheckfoodqualitytominimizepublichazards.Thebookmay beusedasatextbook;however,Iamnotresponsibleforanylossand/ordamagewhilepracticingor usinganyinformationandknowledgeprovidedbythisbook.

RapidDetectionofFoodAdulterantsandContaminants:TheoryandPractice containswideinformationincludingcommonadulterantsandcontaminantsinvariousfoods,standardsandpermissible limitsofdifferentfoodregulatoryauthorities,andrelateddetectiontechniques;itwouldnothave beenpossibletoprepareamanuscriptwithoutthehelpofmycolleagues,Dr.K.Narsaiah,Dr.Pranita Jaiswal,Dr.YogeshKumar,Dr.RahulKumarAnurag,aswellasvariousresearchassociatesinmy laboratory.Isincerelyacknowledgethecontributionofeachofthem.

Iamindebtedforchildhoodcontributionsandteachingofmymother,father,uncle(Lalkaka),and lateelderbrotherinaruralvillage,whichmademereachthisstatusofwritingabookofinternational standing.Thesacrificesofmywife,Bandana,anddaughters,PriyaandPreeti,especiallyduringmy

extramuralprojectsfortheNationalAgriculturalInnovationProjectandNationalAgriculturalScience Fund,whichgavemein-depthunderstandingofthissubject,aregreatlyappreciated.Ithankin advancethereaderswhosendtheirsuggestions,ifany,forfurtherimprovementstofutureversions ofthisbook.

S.N.Jha Ludhiana June28,2015

Table1.1TypeofAdulterantsandContaminants

S.No.TypeSubstancesAdded

1IntentionaladulterantsSand,marble,chips,stone,mud,otherfilth,talc,chalkpowder, water,mineraloil,andharmfulcolor

2IncidentaladulterantsPesticideresidues,droppingsofrodents,larvaeinfoods,orsimilar unwantedmaterials

3MetalliccontaminantsArsenicfrompesticides,leadfromwater,effluentfromchemical industries,tinfromcans,oranysimilarmaterials

Table1.2PhysicalAdulterantsandTheirEffectsonHealth

S.No.PhysicalAdulterantsFoodsCommonlyInvolvedHealthEffects

1Argemoneseeds Argemoneoil

2Artificiallycolored foreignseeds

3Foreignleavesor exhaustedtealeaves, artificiallycolored sawdust

Mustardseeds Edibleoilsandfats

Asasubstituteforcumin seed,poppyseed,black pepper

Epidemicdropsy,glaucoma, cardiacarrest

Injurioustohealth

TeaInjurioustohealth,cancer

4TricresylphosphateOilsParalysis

5RancidoilOilsDestroysvitaminsAandE

6Sand,marblechips, stones,filth Foodgrains,pulses,etc.Damagesdigestivetract

7 LathyrussativusKhesaridal aloneormixed inotherpulses

8Nonfoodgradeor contaminatedpacking materials

Lathyrism(cripplingspastic paraplegia)

AfoodBloodclot,angiosarcoma, cancer,etc.

environmentswherefoodisbeingprepared.Commonphysicalcontaminantsinfoodincludehair,dirt, insects,andevenglass.Foodcanbecontaminatedbyavarietyofdifferentmethods.Ifyouareinafast foodchainorarestaurant,themostcommonmethodofphysicalcontaminationoffoodisthroughdirty hands.Ifhandsremainunwashed,itispossiblethatworkerscouldcontaminateafoodsupply.Foodcan alsobecontaminatedinfactories.Poorsanitaryconditionscantaintfoodeasilyandcausefood poisoning.Somepossiblecommonphysicalcontaminantsinfoodarelistedin Table1.3.

1.1.2 CHEMICALADULTERANTSANDRESIDUES

Chemicaladulterantsarechemicalsandresiduespresentwherethefoodisgrown,harvested,processed,packaged,stored,transported,marketed,andconsumed.Foodgetsadulteratedorcontaminated bytheseharmfulchemicalsbeyondthepermissiblelimitsfixedbyregulators.Chemicalssometimes

Table1.3CommonPhysicalAdulterants/ContaminantsinDifferentFoods

S.No.FoodArticlesAdulterants

1MilkWater,starch,urea,detergent

2Ghee,cottagecheese,condensedmilk, Khoa,milkpowder,etc.

Vegetableoil,syntheticmilk,formalin

Coaltar,dyes

3SweetcurdVanaspati

4RabdiBlottingpaper

5KhoaanditsproductStarch

6 Chhana orpaneerStarch

7GheeVanaspatiormargarine

8ButterVanaspatiormargarine

9EdibleoilProhibitedcolor

10CoconutoilAnyotheroil

11SugarChalkpowder,urea,color

12HoneySugarsolution

13JaggeryWashingsoda,chalkpowder,sugarsolution,metanil (yellowcolor)

14Sweetmeats,icecream,andbeveragesMetanilyellow(anonpermittedcoaltarcolor),saccharin

15Wheat,rice,maize,jawar,bajra,chana, barley,etc.

Dust,pebble,stone,straw,weedseeds,damagedgrain, “weevilled”grain,insects,rodenthairandexcreta

16MaidaResultantattaorcheapflour

17Maida/riceBoricacid

18Wheat,bajra,andothergrainsErgot(afunguscontainingapoisonoussubstance), dhaturakanelbunt

19ParboiledriceMetanilyellow(anonpermittedcoaltarcolor),turmeric (forgoldenappearance)

20ParchedriceUrea

21WheatflourChalkpowder

22Dal,wholeandsplitKhesaridal,clay,stone,gravels,webs,insects,rodent hairandexcreta,metanilyellow(anonpermittedcoaltar color)

23Atta,maida,suji(rawa)Sand,soil,insect,webs,lumps,rodenthairandexcreta, ironfilings

24BajraErgot-infestedbajra

25PulsesLeadchromate

26MustardseedArgemoneseed

27PowderedspicesAddedstarch,commonsalt

28TurmericpowderColoredsawdust

29TurmericwholeLeadchromate,chalkpowder,oryellowsoapstone powder

30ChilipowderBrickpowder,saltpowderortalcpowder,artificialcolor, water-solublecoaltarcolor

31CommonsaltWhitepowder

32TealeavesExhaustedtea

arealsoaddedintenselytoincreasefoods’shelflife,taste,andappearance.Theyalsosometimescome intofoodinsmalleramountsfromtheair,water,andsoil.Someexamplesarearsenic,mercury,and nitrates.Chemicalresiduesinfoodsarecommontodaybecauseoftherampantuseofagrochemicalsin agriculturalpracticesandanimalhusbandrywiththeintenttoincreasecropsandreducecosts.Such agentsincludepesticides(e.g.,insecticides,herbicides,rodenticides);plantgrowthregulators;veterinarydrugs(e.g.,nitrofuran,fluoroquinolones,malachitegreen,chloramphenicol);andbovine somatotropin.Thereisaseparateissueofgeneticallymodifiedfood,orthepresenceinfoodsof ingredientsfromgeneticallymodifiedorganisms.Theimpactofchemicalcontaminantsonconsumer healthandwell-beingisoftenapparentonlyaftermanyyearsofprolongedexposureatlowlevels(e.g., cancer).Chemicalcontaminantscanbeclassified(Tables1.4and1.5)accordingtothesourceof contaminationandthemechanismbywhichtheyenterthefoodproduct.

Table1.4ChemicalContaminantsinFoodsandTheirIllEffectsonHealth

S.No.ContaminantsFoodsCommonlyInvolvedHealthEffects

1Mineraloil(whiteoil, petroleumfractions)

Edibleoilsandfats,black pepper Cancer

2LeadchromateTurmeric(wholeand powdered),mixedspices Anemia,abortion,paralysis, braindamage

3MethanolAlcoholicliquorsBlurredvision,blindness,death

4Diethylstilbestrol(additivein animalfeed) MeatImpotence,fibroidtumors,etc.

53,4-BenzopyreneSmokedfoodCancer

6ExcessivesolventresidueSolventextractedoil, oilcake,etc.

7Nonpermittedcoloror permittedfoodcolorbeyond safelimit

8Butylatedhydroxyanisoland butylatedhydroxytoluene beyondsafelimit

9Monosodiumglutamate(flour) (beyondsafelimit)

10Coumarinand dihydrocoumarin

Possibilityofnumbnessinfeet andhand

ColoredfoodMentalretardation,cancer,other toxiceffects

OilsandfatsAllergy,liverdamage,increase inserumcholesterol,etc.

Chinesefood,meatandmeat products

Braindamage,mental retardationininfants

FlavoredfoodBloodanticoagulation

11FoodflavorsbeyondsafelimitFlavoredfoodChancesoflivercancer

12BrominatedvegetableoilsColddrinksAnemia,enlargementofheart

13Sulfurdioxideandsulfite beyondsafelimit

Inavarietyoffoodsas preservatives

Acuteirritationofthe gastrointestinaltract,etc.

14Artificialsweetenersbeyond safelimit SweetfoodsChanceofcancer

15ArsenicFruitssuchasapplessprayed withleadarsenate

16BariumFoodscontaminatedbyrat poisons(bariumcarbonate)

Dizziness,chills,cramps, paralysis,death

Violentperistalsis,arterial hypertension,muscular twitching,convulsions,cardiac disturbances

Table1.4ChemicalContaminantsinFoodsandTheirIllEffectsonHealth cont’d S.No.ContaminantsFoodsCommonlyInvolvedHealthEffects

17CadmiumFruitjuices,softdrinks,etc.,in contactwithcadmium-plated vesselsorequipment; cadmium-contaminatedwater andshellfish

Increasedsalivation,acute gastritis,liverandkidney damage,prostatecancer

18CobaltWater,liquorsCardiacinsufficiencyand myocardialfailure

19LeadWater,naturalandprocessed foods

Leadpoisoning(foot-drop, insomnia,anemia,constipation, mentalretardation,brain damage)

20CopperAnyFoodVomiting,diarrhea

21TinAnyFoodColic,vomiting

22ZincAnyFoodColic,vomiting

23MercuryMercuryfungicide-treated seedgrainsor mercury-contaminatedfish

Braindamage,paralysis,death

1.1.3 MICROBIOLOGICALANDPATHOGENICCONTAMINANTS

Food-borneillnesscausedbymicroorganismsisalargeandgrowingpublichealthproblem.Most countrieswithsystemsforreportingcasesoffood-borneillnesshavedocumentedsignificantincrease sincethe1970sintheincidenceofdiseasescausedbymicroorganismsinfood,includingpathogens suchas Salmonella, Campylobacterjejuni,andenterohemorrhagic Escherichiacoli,andparasitessuch as Cryptosporidium, Cryptospora,andtrematodes.Someimportantbacterialandfungalcontaminants, andpathogens,incommonlyavailablefoodsandtheirilleffectsonhealtharelistedin Tables1.6 1.8, respectively.

1.1.4 TOXINS

Toxinsaresubstancescreatedbyplantsandanimalsthatarepoisonoustohumans.Toxinsalsoinclude medicationsthatarehelpfulinsmalldosesbutpoisonouswhenusedinalargeamount.Toxinscanbe smallmolecules,peptides,orproteinsthatarecapableofcausingdiseaseoncontactwithorupon absorptionbybodytissues,interactingwithbiologicalmacromoleculessuchasenzymesorcellular receptors.

Naturaltoxinsarechemicalsthatarenaturallyproducedbylivingorganisms.Thesetoxinsarenot harmfultotheorganismsthemselvesbuttheymaybetoxictoothercreatures,includinghumans,when eaten.Someplantshavethecapacitytonaturallyproducecompoundsthataretoxictohumanswhen consumed(HealthCanada,2011).

Mycotoxins areanothergroupofnaturaltoxins.Theword mycotoxin isderivedfromtheGreek wordforfungus, mykes,andtheLatinword toxicum ,meaning“poison.”Mycotoxinsaretoxic chemicalproductsformedbyfungithatcangrowoncropsinthefieldorafterharvest.Foodsthatcan

Table1.7CommonFungalContaminantsandTheirIllEffectsonHealth S.No.FungalContaminantsFoodsInvolvedHealthEffects

1Aflatoxins

2Ergotalkaloidsfrom Claviceps purpurea,toxicalkaloids, ergotamine,ergotoxin,and ergometrinegroups

3Toxinsfrom Fusariumsporotrichioides

4Toxinsfrom Fusarium sporotrichiella

5Toxinsfrom Penicilliuminslandicum, Penicilliumatricum, Penicilliumcitreovirede, Fusarium, Rhizopus, Aspergillus

6Sterigmatocystinfrom Aspergillusversicolour, Aspergillusnidulans,and Bipolaris

Aspergillusflavus-Contaminated foodssuchasgroundnuts, cottonseeds,etc.

Ergot-infestedbajra,ryemeal orbread

Grains(millet,wheat,oats,rye, etc.)

Liverdamageandcancer

Ergotism(St.Anthony’s fire-burningsensationin extremities,itchingofskin, peripheralgangrene)

Alimentarytoxicaleukia (epidemicpanmyelotoxicosis)

MoistgrainsUrovdisease(Kaschin-Beck disease)

YellowriceToxicmoldyricedisease

FoodgrainsHepatitis

7 Ascarislumbricoides Anyrawfoodorwater contaminatedbyhumanfeces containingeggsoftheparasite

Ascariasis

8 Entamoebahistolytica (viral)RawvegetablesandfruitsAmebicdysentery

9Virusofinfectious hepatitis(virusA)

Shellfish,milk,unheatedfoods contaminatedwithfeces,urine, and/orbloodofinfectedhuman

10MachupovirusFoodscontaminatedwithrodent urine,suchascereals

1.1.5.2SeparateRawandCookedMaterials

Infectioushepatitis

Bolivianhemorrhagicfever

•Keeprawmeat,poultry,andseafood,vegetables,andsoonseparatefromotherfoods.

•Useseparateequipmentandutensils,suchasknivesandcuttingboards,forhandlingrawfoods.

•Storefoodincontainerstoavoidcontactbetweenrawandpreparedfoods.

1.1.5.3CookThoroughly

•Besurethatmeatandpoultryjuicesareclearandnotdiscolored.

•Cookfoodthoroughly,especiallymeat,poultry,eggs,andseafood.

•Bringfoodslikesoupsandstewstoboilingtomakesurethattheyhavereached70 C.

•Reheatcookedfoodproperlybeforeeating.

Table1.10OtherFoodContaminantsandTheirHealthEffects

CategoriesContaminantsPotentialHealthConcerns

Microorganisms

Cryptosporidium

Giardialamblia

Heterotrophicplatecount

Disinfectionby-products

Legionella

Total coliforms (including fecalcoliformand Escherichiacoli)

Viruses(enteric)

Brucella

E.coli

Staphylococcus sp.

Streptococcus sp.

Listeria sp.

Mycobacterium tuberculosis

Mycobacteriumbovis

Salmonella

Clostridium

Yeastandfungus

Bromate

Chlorite

Haloaceticacids(HAA5)

· Gastrointestinalillness(suchasdiarrhea, vomiting,andcramps)

· Gastrointestinalillness(suchasdiarrhea, vomiting,andcramps)

· Heterotrophicplatecounthasnohealtheffects; itisananalyticmethodusedtomeasurethe varietyofbacteriathatarecommoninwater.The lowertheconcentrationofbacteriaindrinking water,thebettermaintainedthewatersystemis.

· Legionnaire’sdisease,atypeofpneumonia

· Notahealththreatinitself;itisusedtoindicate whetherotherpotentiallyharmfulbacteriamay bepresent.

· Gastrointestinalillness(suchasdiarrhea, vomiting,andcramps)

· Accordingtopathogenicityofindividual microorganism

· Accordingtopathogenicityofindividual microorganism

· Accordingtopathogenicityofindividual microorganism

· Accordingtopathogenicityofindividual microorganism

· Accordingtopathogenicityofindividual microorganism

· Accordingtopathogenicityofindividual microorganism

· Accordingtopathogenicityofindividual microorganism

· Accordingtopathogenicityofindividual microorganism

· Accordingtopathogenicityofindividual microorganism

· Increasedriskofcancer

· Anemia;nervoussystemeffectsininfantsand youngchildren

· Increasedriskofcancer

Totaltrihalomethanes · Liver,kidney,orcentralnervoussystem problems;increasedriskofcancer

Table1.10OtherFoodContaminantsandTheirHealthEffects cont’d

CategoriesContaminantsPotentialHealthConcerns

Disinfectants

Inorganicchemicals

Inorganicchemicals (pesticides/insecticides/ fungicides/environmental contaminants/processing contaminantsetc.)

Chloramines(asCl2)

Chlorine(asCl2)

Chlorinedioxide(asClO2)

Antimony

Barium

Copper

Cyanide(asfreecyanide)

Fluoride

Mercury(inorganic)

Nitrates(measuredas nitrogen)

Nitrites(measuredas nitrogen)

· Eye/noseirritation,stomachdiscomfort,anemia

· Eye/noseirritation,stomachdiscomfort

· Anemia;nervoussystemeffectsininfantsand youngchildren

· Increaseinbloodcholesterol;decreaseinblood glucose

· Increaseinbloodpressure

· Short-termexposurecausesgastrointestinal distress

· Long-termexposurecausesliverorkidney damage

· PeoplewithWilson’sdiseaseshouldconsult theirpersonaldoctoriftheamountofcopperin theirwaterexceedstheactionlevel.

· Nervedamageorthyroidproblems

· Bonedisease(painandtendernessofthebones); childrenmaygetmottledteeth

· Kidneydamage

· Infantsyoungerthantheageof6monthswho drinkwatercontainingnitratesinexcessofthe MCLcouldbecomeseriouslyilland,if untreated,maydie.Symptomsincludeshortness ofbreathandblue-babysyndrome.

· Infantsyoungerthantheageof6monthswho drinkwatercontainingnitritesinexcessofthe MCLcouldbecomeseriouslyilland,if untreated,maydie.Symptomsincludeshortness ofbreathandblue-babysyndrome.

Selenium · Hairorfingernailloss;numbnessinfingersor toes;circulatoryproblems

Thallium · Hairloss;changesinblood;kidney,intestine,or liverproblems

Acrylamide · Nervoussystemorbloodproblems;carcinogenic

Benzene · Anemia;decreaseinbloodplatelets; carcinogenic

Benzopyrene(polycyclic aromatichydrocarbons)

· Reproductivedifficulties;carcinogeniceffects

Carbofuran · Problemswithblood,nervoussystem,or reproductivesystem

Chlordane · Liverornervoussystemproblems;carcinogenic effects

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