1. Preliminary Analysis by: Fawn Hornsby 1, Charles Rogers 2, & Sarah Thornton 3 1,3 North Carolina State University 2 University of Texas at El Paso Client: Mr. Charles Pietarinen NJ Department of Environment Tuesday, July 25, 2006 @ North Carolina State University Graduate Assistant: Mr. Andrew Moore Faculty Mentor: Dr. William Hunt

2. Overview Background NJDEP Project Dealing with Instrument Peculiarities Previous Analysis Objectives Data Sources Assessment I (Overall) Assessment II (Transport)

3. Background

4. NJDEP Mercury Project The NJDEP established mercury air monitoring sites in Elizabeth and New Brunswick, NJ to better understand this problem Complex and extensive mercury data sets were collected using the Tekran Continuous Mercury Analyzer –Elemental, particulate, and reactive gas mercury were measured at each city during 2004 and 2005.

5. Dealing with Instrument Peculiarities Because of a peculiarity in the way the instrument operates, the mercury levels were measured beginning at random start times after midnight, so that no two measurements were collected during the same time period Each measurement was assigned to one of 24 hourly time blocks based on the midpoint of the observed hour For correlation analysis, observations in New Brunswick and Elizabeth were matched by date and were examined for one to up to 24 hours out of phase.

6. Found Diurnal Patterns and compared with them with other forms of air pollutants. Checked for yearly patterns Utilized meteorological variables to find locations of possible sources. Checked for regional effects between New Brunswick and Elizabeth. Previous Analysis

7. Elemental Mercury Box Plot Without outliers : Reactive Gas Mercury Box Plot Without outliers : Particulate Box Plot Without outliers : ~Finding Diurnal Patterns~ Hourly Patterns Throughout the Day

8. Daily Averages of Elemental Mercury at New Brunswick versus Elizabeth REACTIVE GAS MERCURY WITH Outliers: Correlation: r = 0.514 R-Squared Value: r^2 = 0.2719 Daily Max Hour: Correlation: r = 0.37661 R-Squared Value: r^2 = 0.1418 ELEMENTAL MERCURY WITH Outliers: Correlation: r = 0.1769 R-Squared Value: r^2 = 0.0313 WITHOUT Outliers: Correlation: r = 0.174 R-Squared Value: r^2 = 0.0306 PARTICULATE MERCURY WITH Outliers: Correlation: r = 0.571 R-Squared Value: r^2 = 0.3262 WITHOUT FARTHEST Outlier: Correlation: r = 0.6912 R-Squared Value: r^2 = 0.4778

9. Elemental Mercury: Highest concentrations from 140-170, and 190-220 degrees Source Graphs For Elizabeth Particulate Mercury: Highest concentrations from 180-230 and 240-270 degrees Reactive Gas Mercury: Highest concentrations coming from the directions of: 0-20, 120-160, and 220-280 degrees

10. Elemental Mercury: Highest concentrations from 40-90 degrees Source Graphs For New Brunswick Particulate Mercury: Highest concentrations from 70-100 and 240-290 degrees Reactive Gas Mercury: Highest concentrations coming from the directions of: 60-100, and 200-240 degrees

11. Objectives Analysis I: Re-examine diurnal patterns for the year as well as all seasons. Examine the day of the week effect Explore the relationship between the three phases of mercury, and ozone, temperature, fine particulate matter, and precipitation with emphasis on seasonal variations. Analysis II: Analyze the mercury data in order to determine if pollution transport effects mercury levels in New Brunswick and Elizabeth –Focus on mercury pollution transport to answer a number of questions such as: 1)Is mercury air pollution regional in nature? 2)Do sources affect air monitoring sites in both Elizabeth and New Brunswick simultaneously or are they out of phase by an hour or more?

12. Data Sources Wind speed & direction, temperature, and precipitation were examined along with ozone and fine particulate matter (from USEPA). –Ozone data are measured at two locations: Rutgers University as well as Bayonne, New Jersey –Temperature data was measured at NWS Cooperative Observing Station in New Brunswick and also measured at the Newark Airport in Newark, New Jersey.

13. All Diurnal Patterns use a 50% completeness criteria. High values above 2 standard deviations were removed in order to better see the distributions regarding the seasonal diurnal patterns. The Winter months consisted of December, January, & February for 2004 and 2005. The Summer months consisted of June, July, & August for 2004 and 2005. Analysis I Another Look at Diurnal Patterns

14. Another Look At Diurnal Patterns: Elemental Mercury Yearly Diurnal Patterns in Elizabeth:Yearly Diurnal Patterns in New Brunswick: Summer Ozone Season Elizabeth, 2005

15. Another Look At Diurnal Patterns: Particulate Mercury Yearly Diurnal Patterns in Elizabeth:Yearly Diurnal Patterns in New Brunswick: Summer Ozone Season Elizabeth, 2004

16. Another Look At Diurnal Patterns: Reactive Gas Mercury Yearly Diurnal Patterns in Elizabeth:Yearly Diurnal Patterns in New Brunswick: Summer Ozone Season Elizabeth, 2004

17. Elemental Mercury Values During the Winter Seasons New Brunswick: Elizabeth:

18. Elemental Mercury Values During the Summer Seasons New Brunswick: Elizabeth:

19. Particulate Mercury Values During the Winter Seasons New Brunswick: Elizabeth:

20. Particulate Mercury Values During the Summer Seasons New Brunswick: Elizabeth:

21. Reactive Gas Mercury Values During the Winter Seasons New Brunswick: Elizabeth:

22. Reactive Gas Mercury Values During the Summer Seasons New Brunswick: Elizabeth:

23. Elemental Hg Day of the Week Effect

24. Particulate Hg Day of the Week Effect

25. Reactive Gas Hg Day of the Week Effect

26. Seasonal Variations 2 Seasons Per Year 1.Winter Months: October ~ March 2. Summer Months: April ~ September 4 Seasons Per Year 1.Spring: March ~ May 2.Summer: June ~ August 3.Fall: September ~ November 4.Winter: December ~ February In order to better see the seasonal patterns of ozone and temperature as it relates to each mercury phase, we divided the year into four seasons and two seasons.

27. Examining Temperatures versus Elemental Mercury in New Brunswick Scatter Plot: Box Plot:

28. Seasonal Variations of Elemental Mercury in New Brunswick

29. Ozone versus Elemental Mercury Elizabeth: New Brunswick:

30. Relationship Between Elemental Mercury, Ozone, & Temperature New Brunswick: Elizabeth:

31. Examining Temperatures versus Particulate Mercury in Elizabeth Scatter Plot: Box Plot:

32. Seasonal Variations of Particulate Mercury in Elizabeth

33. Examining Temperatures versus Particulate Mercury in New Brunswick Scatter Plot: Box Plot:

34. Seasonal Variations of Particulate Mercury in New Brunswick

35. Ozone versus Particulate Mercury Elizabeth:New Brunswick:

36. Relationship Between Particulate Mercury, Ozone, & Temperature New Brunswick: Elizabeth:

37. Examining Temperatures versus Reactive Gas Mercury in Elizabeth Scatter Plot:Box Plot:

38. Seasonal Variations of Reactive Gas Mercury in Elizabeth

39. Examining Temperatures versus Reactive Gas Mercury in New Brunswick Scatter Plot:Box Plot:

40. Seasonal Variations of Reactive Gas Mercury in New Brunswick

41. Ozone versus Reactive Gas Mercury Elizabeth: New Brunswick:

42. Relationship Between Reactive Gas Mercury, Ozone, & Temperature New Brunswick: Elizabeth:

43. Mercury versus Precipitation ~Elemental~ ~New Brunswick~ ~Particulate~ ~Elizabeth~

44. Mercury versus Precipitation ~New Brunswick~ ~Reactive Gas~ ~Elizabeth~

45. Particulate Mercury Daily Average Continuous PM fine Measurements versus the Particulate Mercury Daily Averages in New Brunswick Particulate Mercury Daily Average

46. Continuous PM fine Measurements versus the Particulate Mercury Daily Averages BY SEASON in New Brunswick Particulate Mercury Daily Average Summer: April ~ September R-squared = 0.0305 R-value = 0.1746 Winter: October ~ March R-squared = 0.3408 R-value = 0.5838

47. Particulate Mercury Daily Average Continuous PM fine Measurements versus the Particulate Mercury Daily Averages in Elizabeth Particulate Mercury Daily Average

48. Conclusions For both cities, Elemental and RGM have higher concentrations in the Spring and Summer months while Particulate Mercury has the highest concentrations in the Winter and the lowest concentrations in the warmer months. Temperature is positively correlated with Elemental and Reactive Gas Mercury while negatively correlated with Particulate. Precipitation is negatively correlated with all three phases of Mercury. Describe the relationship between the 3 phases of hg and particulate matter and ozone

49. Recommendations When comparing data collected with the Tekran Continuous Analyzer, we recommend assigning each measurement to one of 24 hourly time blocks based on the midpoint of the observed hour Co-locate mercury instruments with fine particulate, ozone, and meteorological variables in order to better understand the physical processes.

50. Preliminary Analysis by: Charles Rogers 1, Fawn Hornsby 2, & Sarah Thornton 3 1 University of Texas at El Paso 2,3 North Carolina State University Client: Mr. Charles Pietarinen NJ Department of Environment Tuesday, July 25, 2006 @ North Carolina State University Graduate Assistant: Mr. Andrew Moore Faculty Mentor: Dr. William Hunt

51. Statistical Methods  Correlation & Regression Analysis  Mercury Species by Wind Direction  Correlation between sites  Means by direction  Mercury species by time difference  Are the sites out of phase by a hr/more? Analysis II

52. County Emissions of Mercury and Mercury Compounds 2004 0-1 18-48 51-58 74-172 Total On-Site Disposal (pounds)

53. Site Emissions of Mercury and Mercury Compounds 2004 90° 180° 270° 90° 180° 270°

54.  Correlation between sites by wind direction  Specifically, the meteorological data from the New Brunswick site  Means by wind direction for each site  Using meteorological data from New Brunswick and Elizabeth Mercury Species by Wind Direction

55. Primary Wind Directions in New Brunswick 90° 180° 270°

56. Elemental Mercury Correlation By Wind Direction Direction using 30 degree increments New Brunswick (wind direction) East-Southeast 90-120°

57. Particulate Mercury Correlation By Wind Direction Direction using 30 degree increments New Brunswick (wind direction) East-Southeast 90-120°

58. Reactive Gas Mercury Correlation By Wind Direction Direction using 30 degree increments New Brunswick (wind direction) South East-Southeast 90-120°150-180°

59. Comparison of Correlations By Direction Using 30 degree increments Elemental Mercury Particulate Mercury Reactive Gas Mercury New Brunswick (wind direction) East-Southeast 90-120°

60. Northeast 60-90°

61. Northeast 60-90°

62. Northeast West-Northwest 60-90° 210-240°

63. Primary Wind Directions in Elizabeth 90° 180° 270°

64. South-Southwest 180-210°

65. South 150-180°

66. South North 0-30° 150-180°

67. Transport by Time Difference Do sources affect air monitoring sites in both Elizabeth and New Brunswick simultaneously or are they out of phase by an hour or more?

68. Particulate Mercury Correlation by Time Difference Hourly Time Difference

69. Particulate Mercury Correlation by Time Difference Hourly Time Difference Wind Direction: 30-60 Degrees N = 49

70. Particulate Mercury Correlation by Time Difference Hourly Time Difference Wind Direction: 210-240 Degrees N = 75 N = 24

71. Particulate Mercury Correlation by Time Difference Hourly Time Difference Wind Direction: 240-270 Degrees N = 85 N = 88 N = 62

73. Hourly Time Difference Particulate Mercury Correlation by Time Difference Wind Direction: 270-300 Degrees N = 54

75. Hourly Time Difference Particulate Mercury Correlation by Time Difference Wind Direction: 300-330 Degrees N = 35

77. Reactive Gas Mercury Correlation by Time Difference Hourly Time Difference

78. Conclusions  Transport appears to be a factor in all mercury levels  Mercury data in New Brunswick and Elizabeth appear to be effected by the same source(s).  Particulate Hg is most likely to show possible transport or similarly be impacted by the same source  Strong relationship between Hg concentrations for some wind directions  When comparing Elizabeth and New Brunswick sites, it appears that sources are effecting both sites simultaneously or one hour out of phase  More likely to be a factor for particulate mercury, followed by reactive gas and then elemental  For New Brunswick, identified signal from the west for both particulate and reactive gas mercury, but there does not appear to be an associated source in the Toxic Release Inventory

79. Recommendations  Further work needs to be done to better understand pollution transport  A closer look at upper meteorological data might provide greater insight into understanding mercury pollution transport

80. Charles R. Rogers crrogers2@utep.edu University of Texas at El Paso Fawn E. Hornsby fehornsb@ncsu.edu North Carolina State University Sarah A. Thornton sathornt@ncsu.edu North Carolina State University

81. Supplementary Slides

82. Continuous PM fine Measurements and Particulate Mercury Daily Averages By Date in New Brunswick Date Particulate Average Continuous PM

83. Continuous PM fine Measurements and Particulate Mercury Daily Averages By Date in Elizabeth Date Particulate AverageContinuous PM

84. _TYPE__NAME_liz_pnb_p MEAN 4.3796.2696 STD 7.05439.37 N 36 CORRliz_p10.219 CORRnb_p0.2191 4 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 5.894211.1636 STD 8.591620.3234 N 53 CORRliz_p10.6767 CORRnb_p0.67671 3 - Hour Correlations 2 - Hour Correlations 1 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 6.528110.4428 STD 12.716821.0924 N 49 CORRliz_p10.8851 CORRnb_p0.88511 _TYPE__NAME_liz_pnb_p MEAN 3.19996.3432 STD 4.85576.805 N 36 CORRliz_p1.6803 CORRnb_p.68031 8 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 0.65934.7309 STD 1.2587.0156 N 28 CORRliz_p10.0372 CORRnb_p0.03721 15 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 5.5878810.9124 STD 5.4935511.0344 N 88 CORRliz_p10.77103 CORRnb_p0.771031

85. _TYPE__NAME_liz_pnb_p MEAN 8.62597.3166 STD 26.47278.1257 N 72 CORRliz_p10.2550 CORRnb_p0.25501 4 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 9.885011.4106 STD 12.721712.2915 N 68 CORRliz_p10.5524 CORRnb_p0.55231 3 - Hour Correlations 2 - Hour Correlations 1 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 8.713211.1960 STD 9.897913.0988 N 75 CORRliz_p10.7135 CORRnb_p0.71351 _TYPE__NAME_liz_pnb_p MEAN 7.35167.9582 STD 11.76939.0109 N 80 CORRliz_p10.6106 CORRnb_p0.61061 8 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 9.85195.6565 STD 35.55415.6003 N61 CORRliz_p10.1901 CORRnb_p0.19011 15 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 5.773612.2600 STD 5.426013.7839 N 24 CORRliz_p10.7574 CORRnb_p0.75741

86. _TYPE__NAME_liz_pnb_p MEAN 10.11659.8097 STD 21.657311.9016 N 85 CORRliz_p10.4014 CORRnb_p0.40141 4 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 11.941687513.5946 STD 24.485616.6164 N 80 CORRliz_p10.4742 CORRnb_p0.47421 3 - Hour Correlations 2 - Hour Correlations 1 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 8.840412.5114 STD 12.273715.2038 N 85 CORRliz_p10.8263 CORRnb_p0.82631 _TYPE__NAME_liz_pnb_p MEAN 8.71619.1974 STD 25.101011.0321 N 88 CORRliz_p10.3453 CORRnb_p0.34531 8 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 6.917910.1641 STD 9.133717.2333 N 69 CORRliz_p10.5862 CORRnb_p0.58621 15 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 10.230512.5281 STD 35.027516.3758 N 37 CORRliz_p10.0125 CORRnb_p0.01251

87. _TYPE__NAME_liz_pnb_p MEAN 3.99418.7185 STD 5.713114.4903 N 30 CORRliz_p10.8197 CORRnb_p0.81971 4 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 5.85459.6329 STD 10.903315.9612 N 36 CORRliz_p10.9358 CORRnb_p0.93581 3 - Hour Correlations 2 - Hour Correlations 1 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 7.540310.5295 STD 16.5440516.0301 N 35 CORRliz_p10.9615 CORRnb_p0.96151 _TYPE__NAME_liz_pnb_p MEAN 2.52395.7642 STD 6.207310.9771 N 31 CORRliz_p10.8997 CORRnb_p0.89971 8 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 2.53736.3306 STD 2.995512.2514 N 21 CORRliz_p1-0.9517 CORRnb_p-0.95171 15 - Hour Correlations _TYPE__NAME_liz_pnb_p MEAN 6.56407.6788 STD 10.57769.8538 N 99 CORRliz_p10.4197 CORRnb_p0.41971