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LEDs

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Potential Environmental Impacts of Light-Emitting Diodes (LEDs):Metallic Resources, Toxicity, andHazardous Waste Classification
S E O N G - R I N L I M ,
D A N I E L K A N G ,
O L A D E L E A . O G U N S E I T A N ,
‡ , §
 A N DJ U L I E M . S C H O E N U N G *
, †
Department of Chemical Engineering and Materials Science,University of California, Davis; School of Social Ecology; and Program in Public Health, University of California, Irvine 
Received April 2, 2010. Revised manuscript received November 3, 2010. Accepted November 12, 2010.
Light-emitting diodes (LEDs) are advertised as environmentallyfriendly because they are energy efficient and mercury-free. This study aimed to determine if LEDs engender otherforms of environmental and human health impacts, and to characterize variation across different LEDs based on colorand intensity. The objectives are as follows: (i) to usestandardized leachability tests to examine whether LEDs are to be categorized as hazardous waste under existing UnitedStates federal and California state regulations; and (ii) touse material life cycle impact and hazard assessment methods to evaluate resource depletion and toxicity potentials ofLEDs based on their metallic constituents. According to federalstandards, LEDs are not hazardous except for low-intensityredLEDs,whichleachedPbatlevelsexceedingregulatorylimits(186 mg/L; regulatory limit: 5). However, according to Californiaregulations, excessive levels of copper (up to 3892 mg/kg;limit: 2500), Pb (up to 8103 mg/kg; limit: 1000), nickel (up to 4797mg/kg; limit: 2000), or silver (up to 721 mg/kg; limit: 500)render all except low-intensity yellow LEDs hazardous. Theenvironmental burden associated with resource depletionpotentials derives primarily from gold and silver, whereas theburdenfromtoxicitypotentialsisassociatedprimarilywitharsenic,copper, nickel, lead, iron, and silver. Establishing benchmarklevels of these substances can help manufacturers implementdesignforenvironmentthroughinformedmaterialssubstitution,canmotivaterecyclersandwastemanagementteamstorecognizeresource value and occupational hazards, and can informpolicymakers who establish waste management policies forLEDs.
Introduction
Light-emitting diodes (LEDs) are emerging as widely dis-tributed sources of lighting because they are advertised ashaving better energy efficiency than other lighting sources,andasbeingmoreenvironmentallyfriendlybecausetheydonotcontainmercury(
1
-
).Itisnotclear,however,whetherthe material content of the LEDs, which generally includegroupIII
-
 Vsemiconductors,presentsitsownsetofpotentialenvironmentalimpacts,especiallywhendisposedofatend-of-life.In the last 10 years, the market for LEDs has increaseddramatically with an expanded diversity in applicationsincluding: colored light applications such as traffic signals,pedestriancrossings,exitsigns,anddecorativeholidaylights;indoor white-light applications such as task lighting; andoutdoor white-lighting such as path lighting (
). In additionto these applications, which use small “indicator” or “pin-type” LEDs, full-size bulbs made with high brightness LEDs(also referred to as high power or high intensity LEDs) arebecoming popular for direct substitution of conventionalbulbsforroomlighting(
-
).Thefocusofthecurrentstudy is on the small indicator type LEDs, because they representa rapidly growing market of products that are widely distributed, making them difficult to manage at end-of-life.Furthermore, because of their small size, relative simplicity,andubiquitoususe,theyprovideanappropriatebenchmarforquantifyingthepotentialenvironmentalimpactofLEDs.The rapid growth in the LED industry implies that,ultimately, LEDs will contribute to the solid waste stream,and could impact resource availability, human health, andecosystemsinmuchthesamewayasgenericelectronicwaste(e-waste) from computers and cell phones has generatedconcern in recent years (
). To put this in context, the U.S.imports over 120 million sets of holiday lights each year,representing 
12billionindividualbulbs,mostofwhichnow consist of LEDs (
); whereas, the U.S. cellular phone salesvolumeinrecentyearshasbeen
200millionunitsannually (
). It should be noted here that cell phones weigh on theorderof 
100
-
200g,whereasbulbsforholidaylightingweighfarless(
10
-
50g),andthattheseproducts,aswellasotherLED-basedlightingandotherelectronicdevices,arecomplesystems,withinwhichthematerialsofconcernmayconstitute just a small fraction of the product’s total weight.Since the principle of LED lighting derives from theapplication of group III
-
 V semiconductors (
), LED chipscancontainarsenic,gallium,indium,and/orantimony(
4,
).These substances have the potential to cause human healthandecologicaltoxicityeffects(
10 
).Furthermore,anLEDchipis assembled into a usable pin-type device through theapplication of leads, wires, solders, glues, and adhesives, as wellasheatsinksforthermaldissipationmanagement(
4,
).Theseancillarytechnologiescontainadditionalmetalssuchas copper, gold, nickel, and lead (Pb). Although organiccompoundssuchasbrominatedflameretardantsmightalsobe used in the transparent plastic housing of LEDs and canbe harmful to the environment, this study is focused on themetals in the LEDs.Thus, the objectives of this study are as follows: (i) to usestandardizedleachabilityteststoexaminewhetherpin-typeLEDsaretobecategorizedashazardouswasteunderexisting United States federal (Toxicity Characteristics Leaching Procedure; TCLP) and California (Total Threshold Limiting Concentrations; TTCL) regulations; and (ii) to use materiallifecycleimpactandhazardassessmentmethodstoevaluateresource depletion and toxicity potentials of pin-type LEDsbased on their metallic constituents. Satisfaction of theseobjectivesshouldprovideguidancetomanufacturerswanting toimplementdesignforenvironment(DfE),andtorecyclersandwastemanagementteamswantingtomaximizeresourcerecoverywhileminimizingoccupationalhazardsduetotoxicexposures.
* Corresponding author phone:
+
1-530-752-5840; fax:
+
1-530-752-9554; e-mail: jmschoenung@ucdavis.edu.
Department of Chemical Engineering and Materials Science,University of California, Davis.
School of Social Ecology.
§
Program in Public Health, University of California, Irvine.
Environ. Sci. Technol.
2011,
45,
320–327
320
9
ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 45, NO. 1, 2011 10.1021/es101052q
2011 American Chemical Society
Published on Web 12/07/2010
 
Materials and Methods
SamplesofLEDsUsedforthisStudy.
Nine 5-mm (T1
-
3/4)pin-type LEDs, purchased from Purdy Electronics Corpora-tion(Sunnyvale,CA)andweighingonaverage
300mgeach, were selected for this study (see Table 1, as well as Table S-1andFigureS-1intheSupportingInformation(SI),fordetails).TheLEDsrepresentvariouscolorsandluminousintensities.The LEDs include various III
-
 V semiconductor materialsthat emit light with a specific range of wavelengths. Detailson these materials, emission wavelengths, as well as otherattributes,includingfullviewingangleandpowerdissipation,are provided in Table 1.The color LEDs are further categorized for the purposeof comparison in this study as having either low or highintensities, relative to each other. The low-intensity colorLEDs(withluminousintensitiesrangingfrom50to400mcd)are suitable for single-LED indicator applications (
); thehigh-intensitycolorLEDs(withluminousintensitiesranging from 900 to 9000 mcd) can be used for lighting applicationssuch as outdoor message signboards (
11
). The white LEDhas a luminous intensity of 10 000 mcd and is suitable foruse in liquid-crystal display (LCD) backlighting and automo-tive applications (
11
).Twenty metals, identified in the next section, wereanalyzed in each LED. The transparent plastic housing wasoutside the scope of this study, but would be interesting future work due to the potential end-of-life implications of managing polymeric materials (
12 
). We used new LEDs forthisworkwiththeunderstandingthatmaterialcontentdoesnot deteriorate with use because LED “burn-out” is causedprimarilybythermo-mechanicalstresses,whichdonotaffectmaterial composition (
).
Determination of Hazardous Waste Potential and Me-tallic Content of LEDs.
To evaluate hazardous wastepotential, two toxicity characterization methods were used:(i) the U.S. Environmental Protection Agency’s TCLP (
13 
), whichisdesignedtoestimatetheconcentrationofsubstancesthat would leach in landfill facilities, as defined by federalregulations; and (ii) the California Department of ToxicSubstances Control’s TTLC method (
14 
), which is used todetermine whether defunct products would be classified ashazardous waste under State of California regulations (seeTable S-2 of the SI for details). The TTLC also provides dataonthemetallicconstituent,whichweuseheretoalsoevaluateresourcedepletionandtoxicitypotentials.TodeterminetheconcentrationofeachmetaldetectedintheTCLPandTTLCprocedures,weusedU.S.EPAmethod6010B(
15 
)forbarium,chromium, copper, nickel, silver, and zinc; and U.S. EPA method6020A(
16 
)foraluminum,antimony,arsenic,cerium,gadolinium, gallium, gold, indium, iron, lead (Pb), mercury,phosphorus, tungsten, and yttrium. The TCLP and TTLCresults were compared to the respective threshold limits toidentify hazardous waste potential.
Evaluation of Resource Depletion and Toxicity Poten-tialsforLEDs.
Evaluationsofresourcedepletionandtoxicity potentials were based on LED metallic content and therespective weighting factors derived from established lifecycle impact-based and hazard-based assessment method-ologies. These methodologies, summarized in Table 2 anddescribed briefly below, represent a diverse set of well-recognizedmethods,eachformulatedonthebasisofuniqueassumptions, models, and data sets. Although each of thesemethods also corresponds to their own individual set of strengths, weaknesses, and inevitable data gaps, when usedcollectively, such as in the present study, the results can beused to provide various stakeholders with a more robustcollection of information for decision-making (
17 
).The formula used to calculate the resource depletion ortoxicity potential associated with each metal is: where
i
is a potential (i.e., life cycle impact-based resourcedepletion potential; hazard-based occupational toxicity potential;hazard-basedToxicPotentialIndicator(TPI);andlife cycle impact-based toxicity potentials for cancer, non-cancer, and ecotoxicity, as listed in Table 2) from metal i;
i
is the content of metal i in the LED (kg/kg);
is the weightof the LED (kg); and
WF 
i
is the weighting factor for thepotential for metal i.For life cycle impact-based resource depletion potential,the weighting factors are the characterization factors forabiotic resource depletion potential derived from the CML2001(
18 
)andEPS2000(
19 
)methodologies.Forhazard-basedoccupational toxicity potential, the weighting factors arederived as the inverse of the exposure limits, i.e., ThresholdLimit Value (TLV)
-
Time Weighted Average (TWA) (
20 
),PermissibleExposureLimit(PEL)
-
TWA(
20 
),andReferenceExposureLimit(REL)
-
TWA(
20 
).Forthehazard-basedToxicPotential Indicator (TPI) (
21, 22 
), the weighting factors arecalculatedfromR-phrase(hazardoussubstancedeclarationssuchasflammability,reactivity,andtoxicity),WaterHazardClass,MaximumAdmissibleConcentration(MAK),EuropeanUnion carcinogenicity, and Technical Guidance Concentra-tion (TRC) data, by using the TPI calculator (
21
).Forlifecycleimpact-basedtoxicitypotential,theweighting factorsarethecharacterizationfactorsforcancer,noncancer,andecotoxicitypotentials,respectively,derivedfromtheToolfor the Reduction and Assessment of Chemicals and otherenvironmental Impacts (TRACI) (
23 
). These evaluations arebasedonthemetalcontentintheLEDs,anddonottakeintoaccount the materials used in the manufacturing processesor the transport pathways for the metals in landfill andincinerator facilities due to the lack of data on distributionratio for metals into flue gas and ashes, as noted in the work byLimandSchoenung(
10 
).Therefore,theresourcedepletionand toxicity potentials represent the best and worst casescenarios, respectively. The total of a given potential for aselect LED was calculated by summing the respectivepotentials of all the metals.
Results and Discussion
Metallic Contents from LEDs.
The results of the TTLCassessment (Table 3) indicate that the LEDs included in thisstudy contain high levels of iron (range: 256 499
-
398 630mg/kg),copper(32
-
3892mg/kg)andnickel(1541
-
4797mg/
TABLE 1
.
Select LED Samples
sample name(color/intensity) red/low red/high yellow/low yellow/high green/low green/high blue/low blue/high white
LED color red red yellow yellow green green blue blue whitesemiconductor material GaAsP InGaAlP GaAsP InGaAlP GaP GaN GaN GaN InGaNpeak emission wavelength (nm) 625 644 590 591 565 525 430 475 n/afull viewing angle (degrees) 30 8 30 6 30 20 10 20 20power dissipation (mW) 105 125 105 125 105 120 140 120 100luminous intensity (mcd) 150 6000 50 9750 50 5000 400 900 10000
i
)
i
·
·
WF 
i
(1)
VOL. 45, NO. 1, 2011 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
9
321
 
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       2       3
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     a
   s
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     a
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     a
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     a
    “   e   q    ”   :   e   q   u    i   v   a    l   e   n    t .
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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 45, NO. 1, 2011

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