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Network Plan Part 14 - NATTS, Toxics, PAMS

5. EPA's National Toxics Program

In general, EPA plans to use ambient air toxics monitoring to support the air toxics program's efforts to reduce human exposure and health risks from air toxics. The monitoring data provided by the ambient air toxics monitoring program is intended to support four major objectives:

  • Establish trends and evaluate the effectiveness of air toxics emissions reduction strategies.
  • Characterize ambient concentrations (and deposition) in local areas. Air toxics originate from local sources and can concentrate in relatively small geographical areas, producing the greatest risks to human health.
  • Provide data to support, evaluate, and improve air quality models. Air quality models are used to develop emission control strategies, perform exposure assessments, and assess program effectiveness.
  • Provide data to support scientific studies to better understand the relationship between ambient air toxics concentrations, human exposure, and health effects from these exposures.

EPA's national air toxics monitoring program is comprised of four different monitoring efforts:

  • National Air Toxics Trends Stations (NATTS)
  • EPA funded local-scale projects to assess conditions at the local level
  • Existing State and local program monitoring
  • Persistent bio-accumulative toxics monitoring

The objective for the NATTS network is to provide long-term monitoring data for certain priority air toxics across representative areas of the country in order to establish overall trends for these pollutants. Currently there are 23 NATTS established in 22 cities. The two New York NATTS sites are located in the Bronx, and Rochester, respectively.

EPA's initial ambient air toxics monitoring pilot studies disclosed that significant variations in pollutant concentrations occurred across a city and that these variations cannot be characterized by a single monitoring site. As a result, EPA decided that local-scale projects consisting of several monitors operated for a period of 1 to 2 years should be incorporated into the national air toxics monitoring strategy. In 2006 New York was awarded a grant for a community air quality air study in Tonawanda which began in July 2007. Hazardous air pollutants (HAPs) and fine particulate matter are measured at 4 locations in the Tonawanda community to address citizen concerns. The field sampling portion of this study was completed in July, 2008.

New York State has been operating a toxics monitoring network since 1990, funded entirely by State monies. Currently there are 11 sites statewide collecting 24 hr canister samples for VOC analysis in a 1 in 6 days interval. See section on NY Toxics Monitoring Network

The monitoring program for persistent bio-accumulative toxics primarily consists of deposition monitoring, not ambient air monitoring. Several monitoring programs operated by various Federal agencies have been established to measure the presence of toxics in various media. In 2010 New York completed an EPA funded community grant study titled "New York State Ambient Mercury Baseline Study" for the measurement of speciated mercury in ambient air, as well as mercury in wet deposition. Instruments at the two study sites are still operating with other funding sources and additional funding is being sought to continue this important monitoring.

In addition to air toxic-specific monitoring activities, several other monitoring programs that are primarily intended to address other air pollution concerns incorporate some aspects of air toxics monitoring. For example, the Photochemical Assessment Monitoring Stations (PAMS) collect data on certain volatile organic compound and carbonyl air toxics. Further, the results of some particulate matter monitoring is speciated (i.e., the individual compounds comprising the particulate matter are analyzed) to identify certain air toxics compounds.

5.1 National Air Toxics Trends Stations (NATTS)

EPA's Urban Air Toxics Program identified 33 high-priority urban air toxics. From these 33 air toxics EPA developed a list of 19 "core" air toxics representing the pollutants for which EPA eventually wants to develop trends information. However, because of limitations in available methodologies, EPA decided that at a minimum, in starting the network, each of the NATTS should monitor for at least 6 of these 19 pollutants. These six pollutants are considered national air toxics "drivers" (i.e., pollutants of concern in all areas of the country).

Table 5.1 NATTS Pollutants of Concern
Required Monitoring Desired Monitoring
1,3-butadiene trichloroethylene
acrolein tetrachloroethylene
arsenic beryllium
formaldehyde nickel
benzene cadmium
hexavalent chromium acetaldehyde
1,2-dichloropropene
carbon tetrachloride
lead
chloroform
manganese
methylene chloride
vinyl chloride

For the two NATTS sites, New York will perform analysis of 42 VOCs (Table 5.2), and 12 carbonyls (Table 5.6). More details on the sampling and analysis are provided in the NY Toxics Monitoring, and Photochemical Assessment Monitoring Stations sections, respectively. In addition, low volume PM10 teflon filters are collected for trace metals analysis using ICP-MS. The targeted metals include: arsenic, beryllium, cadmium, lead, manganese, nickel, antimony, cobalt, and selenium, with the last three being potential future HAPs. Hexavalent chromium sampling commenced in November 2007 at the Rochester and Bronx sites. The cellulose filter samples are shipped to EPA/ERG for laboratory analysis. Recently, EPA determined that area wide Chromium VI monitoring should only be applicable in areas with known sources. Sampling at New York NATTS sites was suspended at the end of June, 2013.

Polycyclic Aromatic Hydrocarbons (PAHs) sampling at the Rochester and IS 52 sites began in July, 2008. The collection media consists of one 110 mm diameter glass microfiber filter and a tubular glass cartridge containing a combination of Polyurethane Foam (PUF) and XAD-2 resin. The exposed samples are shipped to an EPA contract laboratory (ERG) for analysis.

Due to roof construction work at IS 52, sampling for NATTS parameters was temporarily moved to the Morrisania site, 1.7 miles NW of the original location beginning in mid June, 2010. The relocation interrupted some sample collection. The EPA was notified of the temporary relocation prior to the move and the data will be submitted using the AQS code for the Morrisania site: 36-005-0080. The construction work at IS 52 was completed in the summer of 2012, and monitoring resumed at this site in July, 2012.

5.2 NY Toxics Monitoring Network

The NY ambient air toxics monitoring program was first established in 1985 as part of the Governor's Air Monitoring Modernization Capital Budget Program. This monitoring network measures Volatile Organic Compounds (VOCs) across the State. The initial development of the network and analytical capabilities was part of a joint Staten Island/New Jersey Urban Air Toxics Assessment Project (SI/NJ Study) coordinated with U.S. EPA Region II from 1987 through 1989. The network expanded in 1990 to a statewide network.

The goal is to monitor air quality related to toxics in the State's urban, industrial, residential, and rural areas. Implementation of this program starts the development of a long-term toxics air quality database for New York State. The database will be used to define, attain, and preserve good air quality in New York State. The data defines actual air quality impacts of the VOCs. The data is used in the design and management of New York's air quality, including risk assessment, modeling, planning and trend analysis.

Initially, only seventeen VOCs were monitored. In 1995, the number of analytes was increased to nineteen. In 2002, the list of VOCs was further expanded to include 42 compounds as shown in Table 5.2 below:

Table 5.2 Target List of Volatile Organic Compounds
Chemical CAS #
Methylene Chloride 75-09-2
Chloroform 67-66-3
1,2 Dichloroethane 107-06-2
1,1,1 Trichloroethane 71-55-6
Carbon Tetrachloride 56-23-5
Trichloroethylene 79-01-6
1,1,2 Trichloroethane 79-00-5
Tetrachloroethylene 127-18-4
Acrolein 107-02-8
Benzene 71-43-2
Toluene 108-88-3
Ethylbenzene 100-41-4
m,p-Xylene 1330-20-7
o-Xylene 95-47-6
Chlorobenzene 108-90-7
1,2 Dichlorobenzene 95-50-1
1,3 Dichlorobenzene 541-73-1
1,4 Dichlorobenzene 106-46-7
Vinyl Chloride 75-01-4
1,2 Dichloropropane 78-87-5
1,2,4-Trimethylbenzene 95-63-6
1,3,5-Trimethylbenzene 108-67-8
1,1-Dichloroethylene 75-35-4
Hexachloro-1,3-Butadiene 87-68-3
1,1-Dichloroethane 75-34-3
Chloromethane 74-87-3
Chloroethane 75-00-3
cis1,2-Dichloroethylene 156-59-2
cis 1,3-Dichloropropene 542-75-6
trans 1,3-Dichloropropene 542-75-6
Dichlorodifluoromethane 75-71-8
Trichlorofluoromethane 75-69-4
Trichlorotrifluoroethane 76-13-1
Dichlorotetrafluoroethane 76-14-2
1,2-Dibromoethane 106-93-4
A-chlorotoluene (Benzylchloride) 100-44-7
1,1,2,2 Tetrachloroethane 79-34-5
Bromomethane 74-83-9
Styrene 100-42-5
Bromodichloromethane 75-27-4
1,3 Butadiene 106-99-0
Methyl Tert Butyl Ether 1634-04-4
1,2,4 Trichlorobenzene 120-82-1

Volatile organic compounds are collected in stainless steel canisters contained in a sampler known as an ambient air canister sampler. The sampler is an air flow calibrated sampling device that pumps ambient air into the canister. A special stainless steel diaphragm pump provides a constant pressure to push the sample through the sampler. A relief valve is used to maintain a steady pressure for the sample flow controller. Samples are collected at a one in six days frequency and shipped back to the Rensselaer laboratory facility for analysis.

The analysis methodology is a modified version of EPA method TO-15. An aliquot of air sample is taken from the canister at a controlled flow and temperature onto an Entech Model 7100A preconcentrator. The preconcentration process involves a series of steps. The first trap consists of glass beads/Tenax held at -110°C which is then heated to room temperature in order to remove water/moisture in the sample. The next trap in line consists of Tenax held at - 30°C. The contaminants of interest are then desorbed at 150°C and collected on the cryofocuser held at -150°C. The sample is then rapidly heated for column injection using a Varian GC coupled with a Saturn MS detection. This method of analysis allows positive identification by retention time and molecular mass.

Concentration trends charts for some ubiquitous VOCs are provided below.

Note that for 2011, the values shown for IS 52 actually represent those from the site at Morrisania, as all monitoring at IS 52 was relocated to Morrisania in July of 2010 due to roof construction work. In August, 2012 all equipment for NATTS was relocated back to IS 52. The values presented for 2012 represent a composite of the two locations.

Annual Averages for Benzene

Figure 5.1 Annual Averages for Benzene

Annual Averages for Toluene

Figure 5.2 Annual Averages for Toluene

Annual Averages for m,p-Xylene

Figure 5.3 Annual Averages for m,p-Xylene

Annual Averages for o-Xylene

Figure 5.4 Annual Averages for o-Xylene

Annual Averages for 1,3-Butadiene

Figure 5.5 Annual Averages for 1,3-Butadiene

Annual Averages for Dichloromethane

Figure 5.6 Annual Averages for Dichloromethane

Annual Averages for Chloroform

Figure 5.7 Annual Averages for Chloroform

Annual Averages for 1,4-Dichlorobenzene

Figure 5.8 Annual Averages for 1,4-Dichlorobenzene

 Annual Averages for Formaldehyde

Figure 5.9 Annual Averages for Formaldehyde†

Annual Averages for Acetaldehyde

Figure 5.10 Annual Averages for Acetaldehyde

†Note that the toxics monitoring operation at IS 52 was temporarily moved to the Morrisania II site in mid June 2010 due to extensive construction work. In late July 2012, work was completed and monitoring resumed at IS 52. The values shown for 2010 and 2012 represent partial year average only.

Currently there are 11 toxics monitoring sites in operation for the measurement of VOCs, and 8 sites for carbonyls statewide. These locations are shown in Figure 5.12 below.

Location map of toxics monitoring sites

Figure 5.11 Location Map of Toxics Monitoring Sites

5.3 Photochemical Assessment Monitoring Stations (PAMS)

The 1993 revisions to 40 CFR Part 58 provide for the establishment and maintenance of network of air monitoring stations called Photochemical Assessment Monitoring Stations (PAMS) which will supplement the existing State and Local Air Monitoring Stations (SLAMS) network. The selection of parameters to be measured at a PAMS site varies with the site's ozone nonattainment designation and whether a site is upwind or downwind from O3 precursor source areas. These parameters are O3, total oxides of nitrogen (NOx), nitric oxide (NO), nitrogen dioxide (NO2), speciated volatile organic compounds (VOCs) and specific meteorological measurements.

The purpose of the PAMS program is to provide an air quality database that will assist in evaluating and modifying control strategies for attaining the O3 National Ambient Air Quality Standard (NAAQS). PAMS data will also be used to better characterize the nature and extent of the O3 problem, track VOC and NOx emission inventory reductions, assess air quality trends and determine whether areas of New York remain in nonattainment of the O3 NAAQS.

NYSDEC is required to operate and maintain two sites for metropolitan New York. The New York Botanical Gardens PAMS site (located in Northern Bronx) has been operational since 1994. The Queensborough Community College PAMS station (located in Queens) began monitoring of some species in late 1997. The Queens site was fully operational for the 1998 ozone monitoring season. This site moved to Queens College in the spring of 2001 as the QBCC building was undergoing a major renovation and the equipment had to be removed from the site. The Table 5.3 lists the chronology of monitoring at these sites.

Table 5.3 Information on PAMS Sites
Site Name Parameters Implementation
Date
New York Botanical Garden NOx Jun-94
CO Jun-94
O3 Jun-94
VOCs Jun-94
Carbonyls Jun-94
NMOC Jun-99
Meteorology Jun-94
NMOC Sep-99
Queens Community College
closed 12/2001
NOx May-98
CO May-98
O3 May-98
SO2 May-98
VOCs Jun-98
Carbonyls Sep-97
NMOC Aug-98
Queens College NOx Jun-01
CO Jun-01
O3 Jun-01
SO2 Jun-01
Carbonyls Jun-01
NMOC Jun-01

For gaseous parameters, Table 5.4 lists the sampling instruments and analysis methods.

Table 5.4 Instrumentation for Gaseous Pollutants
Parameter Instrument Analysis Method Frequency
NO TECO 42C Chemiluminescent Continuous
NO2 TECO 42C Chemiluminescent Continuous
NOx TECO 42C Chemiluminescent Continuous
O3 TECO 49C Ultraviolet Continuous
CO TECO 48C Infrared Continuous

The following applies to meteorological measurements.

Table 5.5 Equipment for Meteorological Measurements
Parameter Instrument or
Sampling Method
Frequency
Wind Speed SONIC Continuous
Wind Direction SONIC Continuous
Temperature Thermistor Continuous
Relative Humidity Hydroscopic Capacitor Continuous
Barometric Pressure Piezoresistive Sensor Continuous

Carbonyls are sampled using DNPH cartridges and analyzed with HPLC according to EPA Method TO-11a. The target compound list is provided in Table 5.6 below.

Table 5.6 Target Compound List for Carbonyl Sampling
Compound AIRS Code
acetaldehyde 43503
acetone 43551
acrolein 43505
benzaldehyde 45501
crotonaldehyde 43516
formaldehyde 43502
hexanal 43511
methacrolein 43515
m-tolualdehyde 45504
n-butyraldehyde 43510
propionaldehyde 43504
valeraldehyde 43518

Volatile organic compounds are monitored using Summa canisters samples followed by laboratory GCMS analysis as well as by an on-site realtime GC. The methods and sampling frequencies are provided in Table 5.7 below.

Table 5.7 VOC Methods and Sampling Frequencies
Sampling Method Analytical Method Frequency
Method TO-14a GC/FID Hourly
TO-15 (24-hr) GC/MS Every 6 day
TO-15 (40 min) GC/MS Once a week

The targeted compounds are listed below:

Table 5.8 PAMS Target Compounds List
Compound AIRS #
ethene 43203
acetylene 43206
ethane 43202
propene 43205
propane 43204
isobutane 43214
1-butene 43280
n-butane 43212
trans-2-butene 43216
cis-2-butene 43217
3-methyl-1-butene dropped 1995 43282
isopentane 43221
1-pentene 43224
n-pentane 43220
isoprene 43220
trans-2-pentene 43226
cis-2-pentene 43227
2-methyl-2-butene dropped 1995 43227
2,2-dimethylbutane 43227
cyclopentane 43242
4-methyl-1-pentene dropped 1995 43234
cyclopentene dropped 1995 43283
2-,3-dimethylbutane 43284
2-methylpentane 43285
3-methylpentane 43230
2-methyl-1-pentene dropped 1997 43246
n-hexane 43231
trans-2-hexene dropped 1995 43289
cis-2-hexene dropped 1995 43290
n-hexene added 1997 43245
methylcyclopentane 43262
2,4-dimethylpentane 43247
benzene 45201
cyclohexane 43248
2-methylhexane 43263
2,3-dimethylpentane 43291
3-methylhexane 43249
2,2,4-trimethylpentane 43250
n-heptane 43232
methylcyclohexane 43261
2,3,4-trimethylpentane 43252
toluene 45202
2-methylheptane 43960
3-methylheptane 43253
n-octane 43233
ethylbenzene 45203
m,p-xylene 45109
styrene 45220
o-xylene 45204
nonane 43235
isopropylbenzene 45210
n-propylbenzene 45209
m-ethyltoluene added 1995 45212
p-ethyltoluene added 1995 45213
1,3,5-trimethylbenzene 45207
o-ethyltoluene added 1995 45211
1,2,4-trimethylbenzene 45208
n-decane 43238
1,2,3 trimethylbenzene added 1995 45225
1,3-diethylbenzene added 1995 45218
1,4 diethylbenzene added 1995 45219
n-undecane 43954
dodecane added 1997 45218
tnmoc 43102
pamshc 43000

All parameters except for the summer intensive VOCs and carbonyls are run on a continuous basis year round. VOC system startup is scheduled for May 15th each year. The carbonyl's schedule of eight (3 hour) samples every third day ended in September 2005 as the requirement was dropped by EPA to reduce overall cost of the PAMS program. The VOC intensive sampling ends in September after the final system audit. Twenty-four hour carbonyl and canister samples are continued on a six day schedule throughout the year.

The on-site GC system consists of a Markes Unity Air Server-Thermal Desorber System integrated with an Agilent GC. The Summa canisters are shipped to the Rensselaer laboratory facility and analyzed with an Entech preconcentrator with a Varian GCMS System.