fundamentals of formaldehyde and formaldehyde …...2019 iaqa annual meeting formaldehyde this...

IAQA 2018 Annual Meeting

Presenter Company Logo Steve Froelicher, PhD, Senior Scientist

Prism Analytical Technologies

[email protected]

Office Number (989)-772-5088

Fundamentals of Formaldehyde

and Formaldehyde Analysis

2019 IAQA Annual Meeting

Formaldehyde

➢Formaldehyde is the simplest organic molecule containing C, H, and O

➢Formaldehyde is highly reactive

➢Formaldehyde sources are both natural and man-made

➢Formaldehyde exposure is an indoor air quality problem that is frequently overlooked


Formaldehyde

➢This presentation will discuss the impact of formaldehyde on indoor air quality, its sources, and how it can be measured.

➢Acceptable levels in indoor environments will be discussed along with methods to help reduce these levels.


What is Formaldehyde and Why Do We Care

➢ First described in 1855 by Russian scientist

Butlerow

➢ Colorless gas;

➢MW 30; simplest C, H, O molecule

➢ Highly reactive molecule; very versatile for formation of

resins (e.g., phenol-formaldehyde); UF insulation

➢Questions regarding carcinogenicity began in 1980;

phenol – formaldehyde resins began being phased out

(insulation; building materials)


More about Formaldehyde

➢ Formaldehyde (and Acetaldehyde (CH3CHO)) are

present in our bodies as a result of biochemical

processes➢ Formaldehyde formed in “one-carbon cycle”; cellular growth

results in HCHO formation….this is toxic to DNA…instead of

attacking DNA…it is instantly converted into formate ions that

promote further cellular growth

➢ Acetaldehyde…responsible for “hangovers”…created by enzyme

destruction of excess ethanol; excess acetaldehyde is the

primary reason we feel nauseous.

➢ Primary concern: Inhalation


What Encompasses Indoor

Air Quality?

Occupant Comfort(Temperature,

Humidity)

CO, CO2

Particulate-Lifestyle(Skin Cells, Dander, Textile

& Paper Fibers, Smoke)

Particulate-Building(Fiberglass, Corrosion,

Rust)

Volatile Organic

Compounds

(VOCs)

Mold(Spores, Mycotoxins,

MVOCs, Debris)

Indoor

Air

Quality

RadonAllergens

(Pet Dander, Dust

Mites)


Air Quality Statistics

➢VOCs in indoor air 2-5 times higher than outdoor air (EPA)

➢Certain activities may increase VOCs to 1,000 times higher than outdoor air (EPA)

➢Indoor VOCs in winter 3-4 times higher than summer


Causes - Recent Changes

➢Energy efficient building construction

➢Leakage eliminated; traps VOCs in breathing zone

➢Active ventilation is needed

➢Synthetic materials (general increase in VOCs due to MOC (materials of construction))

➢Amount of time spent indoors has increased

➢OVERALL AFFECT: Increase in respiratory conditions


Ventilation ➢ Ventilation concerns (new vs. old homes)

➢ Many older homes are lower in VOCs and

formaldehyde


Situations With IAQ Concerns/Formaldehyde concerns

➢Buying new home

➢Health; VOCs from new construction➢Formaldehyde from adhesives; laminates; coatings

➢ Lumber Liquidators; Weyerhaeser joist coatings

➢Odor

➢Mold


Situations With IAQ Concerns/formaldehyde concerns

➢Change in situation

➢New baby; inferior products containing OSB or other laminates/glues containing formaldehyde

➢New product (e.g., furniture); inferior product construction, especially cabinetry

➢Renovation; glues/adhesives

➢Event (e.g., structural fire); Combustion is a source of formaldehyde; includes fireplace usage


Challenge: Everyone is Different

➢ Depend on:

➢ Specific VOC or type of VOC

➢ Level of exposure

➢ Length of exposure

➢ Individual’s sensitivity

➢ Health Effects

➢ Eye and respiratory irritation, dizziness, headache,

nausea, etc.

No Effect → Irritating → Highly Toxic

www.epa.gov/iaq/voc.htmltoxtown.nlm.nih.gov/text_version/chemicals.php?id=31


What are the Sources of HCHO?

Natural Sources: Wood

Man-Made Sources: Resins; adhesives;

laminates

Combustion Processes (can be

considered a natural source also; forest

fires, etc.)


Sources – Formaldehyde



➢ pine wood

➢ Slow release of formaldehyde; cellulose degradation



➢ Present in many construction materials

➢ Engineered hardwood and bamboo laminate flooring

➢ Cabinetry (urea formaldehyde resins – can off-gas

significantly)

➢ Plywood and OSB (phenol formaldehyde resins – tend

to off-gas less)

➢ Insulation (glass and foam – both urea and phenol

formaldehyde types used)

➢ Produced by combustion sources

➢ Methane (natural gas) converts to formaldehyde due to

incomplete combustion

➢ Furnace, unventilated combustion sources, fireplace,

tobacco smoke



➢ Significant levels found in new or newly renovated homes

➢ Levels

➢ Outdoor: 1-20 ng/L

➢ Indoor: 20-60 ng/L

➢ Symptoms

➢ Causes numerous respiratory issues

➢ Common: irritation of throat, nose, eyes, skin;

exacerbate asthma

➢ Classified as Group 1 carcinogen (IARC): carcinogenic

to humanswww.cdc.gov/nceh/ehhe/trailerstudy/pdfs/08_118152_compendium-for-states.pdfmonographs.iarc.fr/ENG/Monographs/vol100F/mono100F-29.pdf


Consider Health Effects:Range of Particle Sizes for Pollutants

➢ Formaldehyde diameter ~ 0.0001 um

➢ VOCs typically too small in diameter to be trapped by traditional

filtration devices (carbon bed adsorbents needed)


Health Effects –

Formaldehyde


Interesting Dilemma: Product Formulations Containing Formaldehyde

➢ In the presence of water, formaldehyde is in equilibrium with methylene glycol (different CAS Number)

➢ Methylene glycol exists in hair conditioning products (heavily used in hair salons)

➢ Methylene glycol considered nonhazardous

CAS 50-00-0 CAS 463-57-0Hazardous generally nonhazardous


Formaldehyde/Methylene Glycol Equilibrium


How is Formaldehyde Detected?

DNPH Method

2,4-dinitrophenylhydrazine

Not specific to formaldehyde; requires chromatographic separation

Hantzsch Method

in situ generation of fluorescing agent

Very specific for formaldehyde (minor interferences)

Photoacoustic infrared spectroscopy

Mid-IR fundamental spectral absorption line of formaldehyde

Highly specific for formaldehyde


DNPH Method

Requires cold storage

Formaldehyde is derivatized in the DNPH tube

Requires Cold packing and shipping


DNPH Method

The DNPH method for formaldehyde requires a

chromatographic separation.

The method will detect other interfering species

such as aldehydes and ketones


Hantszch Reaction

• In situ derivatization of formaldehyde

• liquid phase reaction of formaldehyde with

acetyl-acetone (2,4-pentadione) and ammonia.

• This reaction produces 3,5-diacetyl-1,4-

dihydrolutidine (DDL) (absorbs light at 410 nm;

fluoresces at 510 nm.


Instrumentation

AL 4021 Aero Laser Fluorimeter


Instrumentation


Potential Interferences are Minimal

minimally sensitive to other aldehydes and ketones

Benzaldehyde < 1 : 20000 Glyoxal < 1 : 123 Butanol < 1 : 900

NO < 1 : 300000 CH3CHO < 1 : 10000 Methanol < 1 : 50000

HNO3 < 1 : 1000 NO2 < 1 : 500000 Acrolein < 1 : 10000

H2O2 < 1 : 100 Acetone < 1 : 300000 SO2 < 1 : 300000

Propanal < 1 : 20000 O3 < 1 : 800 Isobutane < 1 : 300000


Comparison of Methods

Prism TDT Method NIOSH 2016 using DNPH

Formaldehyde collection Adsorption onto thermal desorption

tube

Derivatization on cartridge at testing location

Derivatization Reaction Hantzsch Reaction in situ in instrument

prior to detection

Dinitrophenyhydrazone Reaction on cartridge

Formaldehyde Detection Fluorescence using fluorimeter UV using HPLC separation method

Shipping Method Ambient (no special precautions) Shipped on Ice

Minimum detection limit 0.030 ug (30 ng) 0.1 ug (100 ng)

Volume sampled 4 – 6 L 15 L

Working Range 5 ng/L - ~ 2400 ng/L 15 ng/L – 2450 ng/L


Comparison of Methods


Photoacousic Spectroscopy

Uses the Mid-IR fundamental spectral absorption line of formaldehyde

Highly specific for formaldehyde

Experimental methods currently under development


Results from ~ 6900 Samples


Concentration Units

Concentration: normalized amount of chemical

substance

ng/L nanogram per liter

mg/m3 microgram per cubic meter

mg/m3 milligram per cubic meter

ppm parts per million

ppb parts per billion

Conversions

1 ng/L = 1 mg/m3 = 0.001 mg/m3 or 1 mg/m3 = 1000 mg/m3

1 ppm = 1000 ppb or 1 ppb = 0.001 ppm

Need molecular weight to convert

1 ng/L of Benzene * 24.04 / 78 = 0.3 ppb Benzene


Definitions & Meanings

Exposure Limit: concentration below which workers will not generally

experience adverse effects

PEL: Permissible Exposure Limit

REL: Recommended Exposure Limit

TLV: Threshold Limit Value

IDLH: Immediately Dangerous to Life or Health

Concentration below which escape without injury or irreversible health

effect

TWA: Time Weighted Average

Typically 8 hour work day in 40 hour work week

C: Ceiling

May not be exceeded at any time

ST or STEL: Short Term Exposure Limit

Typically 15 minute period

Ca: potential occupational Carcinogen

Exposure Limits:


Exposure Guidelines and Limits = CONFUSION!!!

Different organizations have posted different limits of

exposure and consumers and professionals alike are

confused by what the real limits are.

• NIOSH lists the lowest limit of 16 ppb for

occupational recommended exposure limit (REL)

• Ambient air can be 5-20 ppb depending on

location


Exposure Guidelines and Limits = CONFUSION!!!

• Most organizations suggest 80-100 ppb and 40-50 ppb

for short term and long term exposures, respectively

• OSHA has established a workplace permissible exposure

limit (PEL) of 940 ng/L (750 ppb)….THIS IS LAW


Exposure Limits – Residential No requirements for residential buildings

Guidelines for green homes

LEED for businesses (37 ug/m3)

4 hr testing (DNPH); other testing devices being

considered

Recommendations available from some states for

select compounds

Formaldehyde

Large range – from 8 ppb to 100 ppb

CA CREL (Chronic Reference Exposure Levels)

www.oehha.ca.gov/air/Allrels.html

Vapor intrusion guidelines


What is CARB-2 Testing?

California Air Resources Board (CARB)

NOTE: CARB-2 testing is for product compliance

• CARB-2

• Short-hand term for airborne toxic control measure

(ATCM) to reduce formaldehyde emissions from wood

products

• Phase 2; 93120 refers to sections in the California

Code of Regulations.

• CARB-2 specifies a primary method ASTM E1333-96

(2002) – large chamber testing method

• ASTM has a small scale chamber version as well

(ASTM D6007-02)


CARB-2 Testing

Typical emission standards for different wood

materials:

• 50 ppb – hardwood/plywood veneer core

• 50 ppb – hardwood/plywood composite core

• 90 ppb – particleboard

• 110 ppb – Medium density Fiberboard (MDF)

• 130 ppb – thin MDF


CARB-2 Testing vs. Room Testing

Often there is confusion regarding CARB-2 Testing

results vs. Room Testing Results

CARB-2 Testing if for one specific laminated board heated in a

chamber under very controlled temperature and humidity

conditions.

Room Testing uses a sampler such as a thermal desorption

tube….represents a “snap-shot” in time of the formaldehyde

concentration in a room from “ALL” sources of formaldehyde

…the results of room testing are dependent on factors of

temperature, humidity, and ventilation rates


Case ScenariosCase 1: Laminate board does not pass CARB-2 testing (i.e.,

material emissions are elevated)

• Installed in home

• Temperature and humidity are relatively low

• Air flow is relatively high

• Room testing of formaldehyde may lead to relatively low number

relative to CARB-2 test results

Case 2: Laminate board passes CARB-2 testing

• Installed in home

• High temperatures and high humidity

• Poorly ventilated area

• Room testing of formaldehyde is relatively high compared to CARB-

2 test results


Environmental

Conditions➢ Temperature

➢ Higher → more VOCs; higher formaldehyde levels

➢ Lower → fewer VOCs

➢ Humidity

➢ Higher → more VOCs; higher formaldehyde levels

➢ Lower → fewer VOCs

➢ Air Flow

➢ Higher → fewer VOCs; lower formaldehyde levels

➢ Lower → more VOCs


Caution: Whole House Ozonation

➢ Odor issues; Allergens

➢ Ozone generators are used to cleanse the

environment of allergens, smoke particulates,

odors, etc.

➢ Potential Issues:

➢ Ozone creates formaldehyde; ozone attacks

double bonds

➢ Collateral damage to materials of construction


Case Study

➢ Client of an Inspector was not happy with 50 ng/L

formaldehyde in RV

➢ Inspector Ozonated the RV for 24 hrs

➢ Formaldehyde levels climbed to beyond 200 ng/L

after ozonation

➢ Ozone attacks double bonds in MOC and can

result in formaldehyde and an entire series of

aldehydes up to C12 (Dodecanal); VOC results

were also elevated after ozonation

➢ Caution on use of ozone generating machines


Other Air Filtration Technology

➢ Rule number 1 (if feasible):

➢ Remove the source of formaldehyde

➢ Safest filtration technology involves use of a

carbon bed adsorbent

➢ Still many unknowns with PCO technology and

other filtration devices that use destructive

mechanisms for odor and VOC removal


Conclusions

➢ Formaldehyde is everywhere due to presence of natural

resources and man-made resources (building products, etc.

➢ Formaldehyde results in symptoms ranging from

respiratory distress and nasal irritation to exacerbation of

asthmatic conditions.

➢ Various methods can be used for detecting formaldehyde,

including DNPH, the Hantzsch Reaction; and Photoacoustic

Infrared spectroscopy


Acknowledgements

Alice Delia, Analytical Laboratory

Manager, Prism

Contact information:Steve Froelicher – Prism Analytical Technologies

[email protected] 989-772-5088


Useful Online Resources

ATSDR: Agency for Toxic Substances and Disease Registry www.atsdr.cdc.gov/

IRIS: Integrated Risk Information System www.epa.gov/iris/index.html

TOXNET: Toxicology Data Network toxnet.nlm.nih.gov/

Can search multiple databases

NIOSH: National Institute for Occupational Safety and Health www.cdc.gov/niosh/

CARB: California Air Resources Board www.arb.ca.gov

US EPA Indoor Air Quality (IAQ) www.epa.gov/iaq/

Household Products Database householdproducts.nlm.nih.gov/index.htm

http://www.atsdr.cdc.gov/

http://www.epa.gov/iris/index.html

http://toxnet.nlm.nih.gov/

http://www.cdc.gov/niosh/

http://www.arb.ca.gov/

http://householdproducts.nlm.nih.gov/index.htm


Questions?

Steve Froelicher

[email protected]

fundamentals of formaldehyde and formaldehyde …...2019 iaqa annual meeting formaldehyde this...

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