# Presentation: 368339

##    What do the Numbers Mean?

- Where do we go from here?

## Show me currenttrends in VOC airpollutant levels...                                                                    

-   [Using Miami-Dade County      Ambient Air Levels  of 40 VOC toxicants monitored over 3 consecutive years.]

## Slide 3

## Hazardous Air Pollutants Detected

-  **11 DiClEthane                   11 DiClEthene**
** ****111 TriClEthane                112 TriClEthane**
** ****1122 TetClEthane             12 DiBrEthane**
** ****12 DiClBenzene                 12 DiClEthane**
** ****12 DiClPropane                 124 TriClBenzene**
** ****124 TriMetBenzene           13 Butadiene**
** ****13 DiClBenzene                 135 TriMetBenzene**
** ****14 DiClBenzene                  Acrylonitrile**
** ****Benzene                              Bromomethane**
** ****Carbon Tetrachloride        Chlorobenzene **

## Hazardous Air Pollutants Detected                                                   (cont’d.)

-  **Chloroethane               Chloroform**
** ****Chloromethane            **_***cis ***_**12DiClEthene**
** **_***cis***_*** *****13DiClPropene        DiClDiFlMethane**
** ****Ethylbenzene                Freon****®**** 11**
** ****Freon****®**** 113                   Freon****®**** 114**
** ****HexCl13Butadiene       **_***meta***_***+***_***para***_** Xylene**
** ****Methylene Chloride      **_**ortho**_** Xylene**
** ****Styrene                          TetClEthene**
** ****Toluene                          **_***trans ***_**12DiClPropene**
** ****TriClEthene                    Vinyl Chloride**

## Trends in Ambient Air Levels of VOCs:    

-                Data collected over three
-              consecutive years were
-          subjected to trend analyses.
-          (When 1-3 data points seemed
-         abnormally high, a second analysis
-           was performed substituting the
-          3-year average for those values.)

## Concentration Trends of         Several Types of VOCs: 

**Refrigerants  (Coolants)**
**Automobile Fuel Vapors**
**Miscellaneous Toxicants**
**Toxicants Flat ****or ****on the**** ****Rise****  **

##  Refrigerants (Coolants)

- Freon®  11
- Freon®  12
- Freon® 113
- Freon® 114
- Chloromethane

##     Refrigerant Freon® 11  slope = 0.00008; 3-yr range = 0.10 ppbv 

##     Refrigerant Freon® 12  slope = 0.00004; 3-yr range = 0.05 ppbv 

##     Refrigerant Freon® 113 slope = -0.000008; 3-yr range = -0.01 ppbv 

##   Refrigerant Freon® 114 slope = -0.00005; 3-yr range = -0.05 ppbv 

## Refrigerant Chloromethane                                          slope = -0.0035; 3-yr range = -3.0 ppbv 

## Automobile Fuel Vapors

**Benzene**
**Toluene**
**Ethylbenzene**
***ortho *****Xylene**
***meta+para*****  Xylenes**
**1,2,4-Trimethylbenzene**

##          Benzene Vapors slope = -0.000007; 3-yr range = -0.02 ppbv 

##          Toluene Vapors slope = 0.000008; 3-yr range = 0.00 ppbv 

-          _Toluene Vapors_ slope = 0.000008; 3-yr range = 0.00 ppbv

##      Ethylbenzene Vapors slope = -0.00001; 3-yr range = -0.02 ppbv 

-      _Ethylbenzene Vapors_ slope = -0.00001; 3-yr range = -0.02 ppbv

##      ortho Xylene Vapors slope = -0.00006; 3-yr range = -0.07 ppbv 

##   meta+para Xylene Vapors slope = -0.0002; 3-yr range = -0.03 ppbv 

*  *_*meta+para*__* *__Xylene Vapors_ slope = -0.0002; 3-yr range = -0.03 ppbv

## 1,2,4-Trimethylbenzene Vapors slope = 0.000005; 3-yr range = 0.00 ppbv 

- _1,2,4__-Trimethylbenzene Vapors_ slope = 0.000005; 3-yr range = 0.00 ppbv

## Miscellaneous Toxicants

- Methylene Chloride
- Styrene

## Methylene Chloride Vapors slope = -0.0015; 3-yr range = -3.00 ppbv 

## Modified Methylene Chloride Plot   slope = -0.00007; 3-yr range = -0.01 ppbv 

##          Styrene Vapors slope = 0.00003; 3-yr range = 0.03 ppbv 

## VOCs Showing Gradual Conc. Decrease

- Methylene chloride
-    **(its decrease already discussed)**
*   **ortho* - Xylene

##            ortho – Xylene  slope = -0.00006; 3-yr range = -0.07 ppbv 

## VOCs Showing Neither Increase Nor A Decrease in Ambient Air Concentration

- Chloroform
- Carbon Tetrachloride
- 1,1,1-Trichloroethane
- 1,3,5-Trimethylbenzene

##            Chloroform slope = 0.00003; 3-yr range = 0.04 ppbv 

##      Carbon Tetrachloride slope = -0.000002; 3-yr range = -0.005 ppbv 

##     1,1,1-Trichloroethane slope = 0.00002; 3-yr range = 0.01 ppbv 

##    1,3,5-Trimethylbenzene  slope = 0.00008; 3-yr range = 0.09 ppbv 

## VOCs Showing Gradual Conc. Increase

**Hexachloro-1,3-butadiene**
**All 3 Dichlorobenzenes (*****o*****,**** *****m*****,**** ****&**** *****p*****)**
**1,1,2,2-Tetrachloroethane**
**Acrylonitrile**
**Vinyl chloride**

##    Hexachloro-1,3-butadiene   slope = 0.0004; 3-yr range = 0.50 ppbv 

##    ortho – Dichlorobenzene  slope = 0.0004; 3-yr range = 0.40 ppbv 

##  1,1,2,2-Tetrachloroethane  slope = 0.0002; 3-yr range = 0.24 ppbv 

##            Acrylonitrile slope = 0.0002; 3-yr range = 0.20 ppbv 

##           Vinyl chloride slope = 0.0002; 3-yr range = 0.20 ppbv 

## Summary of Miami-Dade Trends

- Despite a **tremendous** influx of new residents, ambient air levels of common refrigerants **have not increased**** **over   **0.1 ppbv** during the past three years.
-   Moreover, **three** coolants have actually **decreased** between **0.01 ppbv and****    ****3.0** **ppbv** during this same timeframe.

## Summary of Miami-Dade Trends                                      (cont’d.)

- Despite a large increase in Miami-Dade auto ownership,   ambient air levels of common  refueling vapors   **have not** **increased  greater than 0.02 ppbv.**
- And  **three**  have actually  **decreased** **between  0.02 ppbv and 0.07 ppbv**.
- [An earlier  **Risk Assessment**  sent to  the EPA reported  **only benzene** to be    of possible human health concern.]

## Summary of Miami-Dade Trends                                      (cont’d.)

- Ambient air levels of Methylene Chloride have  **decreased about 3.0 ppbv** and air concentrations of Styrene have only **increased about 0.03 ppbv****.**
- [In this analysis,** ****three-year increases of less than 0.20 ppbv have been considered to be insignificant****.] **

## Summary of Miami-Dade Trends                                      (cont’d.)

**Only Five** of the 40 VOCs commonly detected exhibited **a significant increase** over the past **three years**.  **They should be more closely watched...** ***in case their ambient levels reach*** ***those thought to lead to human health effects:***
**Hexachloro-1,3-butadiene     ****up**** 0.50 ppbv**
***ortho*** ***– *****Dichlorobenzene         ****up**** 0.40 ppbv**
**1,1,2,2-Tetrachloroethane     ****up**** 0.24 ppbv**
**Acrylonitrile                             ****up**** 0.20 ppbv**
**Vinyl chloride                           ****up**** 0.20 ppbv**

## Predicted Future Ambient Air Levels

- _ __If Current Increases Continue 15 Years:_
**Hexachloro-1,3-butadiene    will reach  2.5  ppbv**
***ortho*** ***– *****Dichlorobenzene        will reach  2.0  ppbv**
**1,1,2,2-Tetrachloroethane    will reach  1.2  ppbv**
**Acrylonitrile                             will reach 1.0  ppbv**
**Vinyl Chloride                          will reach 1.0  ppbv **
_**Should we be concerned as to human health?**_

## Hexachlorobutadiene  is on the NIOSH list of     suspected carcinogens because it has the potential to cause kidney &/or lung cancer. The  ACGIH  TLV  is  20 ppb.   A  group  of 205 vineyard workers who were exposed seasonally to hexachlorobutadiene   (0.8-30 mg/m3 in the air over the fumigated zones) showed multiple toxic effects contributing to the development of hypotension, cardiac disease, chronic bronchitis, disturbances of    nervous functions,  and chronic hepatitis.

## The dichlorobenzenes probably have very low human toxicity. They primarily cause injury to the liver and,  secondarily, to the two kidneys.  Central nervous system depression  occurs at concentrations  that are extremely irritating to the eyes and nose.  Upon dermal contact, they may produce a burning sensation.

**Notes:**
The

##  Persons with existing liver trouble or obesity have a greater susceptibility to the effects of 1,1,2,2-tetrachloroethane.    Acute symptoms include eye/nasal irritation, headache,  and nausea. This may progress to cyanosis, central nervous system (CNS) depression, and even unconsciousness or coma within a few hours.  Chronic symptoms include CNS depression and  gastric/hepatic  damage.   The PEL is 5    ppm / 8 hr. period. The ACGIH  TLV is 2 ppm. 

**Notes:**
Persons

##             eye irritation,  headache,  nausea, and weak- ness.   Serious exposures may result in asphyxia and death.  The order of onset of symptoms is weakness in the limbs, dyspnea, burning sensation in the throat, dizziness  and impaired judgement,  cyanosis  and nausea,  irregular breathing,  seizures,  and death.  Seizures  and  cardiac arrest  may  occur  without warning.  Chronic exposures have been associated with liver damage.    Acrylonitrile   is a suspected human carcinogen.     

-             **eye irritation**,  **headache**,  **nausea,** and **weak-** **ness**.   **Serious** exposures may result in **asphyxia** and **death**.  The order of onset of symptoms is **weakness **in the limbs, **dyspnea**, burning sensation in the throat, **dizziness**  and **impaired judgement**,  **cyanosis**  and **nausea**,  **irregular breathing**,  **seizures**,  and **death**.  **Seizures  **and  **cardiac arrest**  may  occur  **without** **warning**.  **Chronic** exposures have been associated with **liver damage**.    Acrylonitrile   is a **suspected human carcinogen.****    **** **

**Notes:**
Mild exposures to acrylonitrile 

## “Vinyl chloride”  disease results if exposure exceeds the allowable limits of concentration. It is narcotic in high concentrations, and it causes liver and kidney damage.  Dermal contact may cause frostbite.  The ACGIH TLV is 5 ppm. The OSHA PEL is 1 ppm for an 8-hr period of exposure.  The human lethal dose is 20,000 ppm.  Vinyl chloride is a known carcinogen.  

**Notes:**
“Vinyl Chloride” disease

## 16 Un-discussed VOCs Not Increasing*                                      More Than 0.15 ppbv Over 3 Years:

- 11 DiClEthane             11 DiClEthene
- 112 TriClEthane	   12 DiBrEthane
- 12 DiClEthane	           12 DiClPropane
- 124 TriClBenzene	   124 TriMeBenzene
- 13 Butadiene		   Bromomethane
- Chloroethane		   *cis *12 DiClEthene
- TetClEthene*******	**	   *cis *13 DiClPropene
- TriClEthene		   *trans *13 DiClPropene
-            ***(Except TetClEthene at 0.18 ppbv increase.)**

##   VOCs Not Increasing > 0.18 ppbv Over 3 Years:                                 (Perdue Data)  Volatile Compound                Ref. No.      3-Year Increase (ppbv)

**112 TriClEthane****	****            43820****	****	****         0.15**
**12 DiBrEthane                       43843****	****	****         0.15**
**12 DiClEthane****	****            43815****	****	****         0.11**
**11 DiClEthane                        43813                           0.01                     **
**12 DiClPropane                      43829****	****	****         0.10**
**124 TriClBenzene****	****            45810****	****	****         0.00**
**124 TriMeBenzene****	****            45208****	****	****         0.05**
**13 Butadiene****	****            43218****	****	****         0.13**
**Bromomethane                      43819****	****	****         0.15**
**Chloroethane****	****            43812****	****	****         0.09 ***** ***
***cis *****12 DiClEthene                  43839****	****                       0.11**
**TetClEthene                           43817****	****	****         0.18                   **
**11 DiClEthene****	****            43826****	****	****         0.11**
***cis *****13 DiClPropene                43831****	****                       0.11**
**TriClEthene****	****	****            43824****	****	****         0.15**
***trans *****13 DiClPropene           43830****	****	****         0.05**

## VOCs Not Increasing > 0.19 ppbv Over 3 Years:                               (WASA Data)                                                                                            Volatile Compound               Ref. No.  3-Year Increase (ppbv)

**12 DiBrEthane                       43843****	****	****         0.18**
**12 DiClEthane****	****            43815****	****	****         0.15**
**11 DiClEthane                       43813                            0.16                     **
**12 DiClPropane                     43829****	****	****       - 0.05**
**124 TriMeBenzene****	****            45208****	****	****         0.04**
**13 Butadiene****	****            43218****	****	****         0.18**
**Bromomethane                     43819****	****	****         0.12**
**112 TriClEthane****	****            43820****	****	****         0.17**
**Chloroethane****	****            43812****	****	****         0.19  ***** ***
***cis *****12 DiClEthene                  43839****	****                       0.13**
**TetClEthene                           43817****	****	****         0.09                   **
**11 DiClEthene****	****            43826****	****	****         0.13**
***cis *****13 DiClPropene                43831****	****                       0.10**
**TriClEthene****	****	****            43824****	****	****         0.14**
***trans *****13 DiClPropene           43830****	****	****         0.19**

## Dual Summary of M-D Trends

**The same 5 VOC’s exhibited similar,  significant increases  over the past three (3) years at both sampling locations:**
-  **       *****  ***
***                                                       ***_**Perdue Site**_**         **_**WASA Site**_
**Hexachloro-1,3-butadiene    up 0.50 ppbv     up 0.58 ppbv**
***ortho*** ***– *****Dichlorobenzene       up 0.40 ppbv     up 0.36 ppbv**
**1,1,2,2-Tetrachloroethane    up 0.24 ppbv     up 0.21 ppbv **
**Acrylonitrile                            up 0.20 ppbv     up 0.21 ppbv**
**Vinyl chloride                          up 0.20 ppbv     up 0.20 ppbv**

##            Sooooooooo...

** **
**  ****W****h****a****t**** ****d****o**** ****t****h****e**** ****N****u****m****b****e****r****s**** ****M****e****a****n****?**
-  **W****h****e****r****e**** ****d****o**** ****w****e**** ****g****o**** ****f****r****o****m**** ****h****e****r****e****?**

## Previous studies indicated that the average values of VOCs at the 2 MD sampling sites only differ by 15 % or less.  This would suggest that the ambient air levels over the county are being measured.   If this is so, combination plots  using all of the pollutant  levels  for each chemical is not farfetched, so trend analysis plots  using  this approach  follow:  

##  Five Refrigerants Combinedslope = 0.00005; 3-yr range = 0.05 ppbv

## All Gasoline Vapor Levels Combined   slope = 0.00008; 3-yr range = 0.10       

## All 1,1,2,2-Tetrachloroethane Levels Combined        slope = 0.0002; 3-yr range = 0.22 ppbv

## All Hexachloro-1,3-butadiene Levels Combined slope = 0.0005;  3-yr range = 0.52 ppbv

##         All Dichlorobenzene Levels Combined        slope = 0.0003; 3-yr range = 0.34 

##          All Acrylonitrile Levels Combined     slope = 0.0002;  3-yr range = 0.20

## All Vinyl Chloride Levels Combined slope = 0.0002; 3-yr range = 0.20 ppbv

## Slide 61

## Slide 62

## VOCs Which May be on a Significant Rise in             the  Ambient Air  Over  Miami-Dade County  

**                                                      ****3-yr inc.**
**                                                        ****(ppbv)**
**Acrylonitrile                                 0.20**
**Chlorobenzene                            0.24**
**1,1,2,2-Tetrachloroethane         0.22**
***o *****-, *****m *****- & *****p *****–Dichlorobenzene   0.34**
**1,2,4-Trichlorobenzene              0.70**
**Hexachloro-1,3-butadiene         0.52**
**Vinyl Chloride                              0.20**

##             Sooooooooo...

**  ****W****h****a****t**** ****d****o**** ****t****h****e**** ****N****u****m****b****e****r****s**** ****M****e****a****n****?**
-    **W****h****e****r****e**** ****d****o**** ****w****e**** ****g****o ****f****r****o****m**** ****h****e****r****e****?**