Ô nhiễm khí thải xe cộ ở Lake Tahoe - Nghiên cứu đất và trầm tích Nevada California

University of Nevada Reno Implications of vehicle emissions in Lake Tahoe soils and sediments A thesis submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Environmental Science and Health By: Veronica Edirveerasingam Dr. Miller/ Dissertation Advisor August, 2006 UMI Number: 3239872 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted.

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ProQuest Information and Learning Company 300 North Zeeb Road P. Box 1346 Ann Arbor, MI 48106-1346 UNIVERSITY OF NEVADA THE GRADUATE SCHOOL RENO We recommend that the dissertation prepared under our supervision by VERONICA EDIRVEERASINGAM entitled Implications of vehicle emissions in Lake Tahoe soils and sediments be accepted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY. - Committee Member Rebel 5 Qual,Member Robert G. , Committee Nee Mark J.

, Committee Member eoC.(Graduate School Representative ha L2 ee LSS CE Marsha H., Associate Dean, Graduate School ABSTRACT This study examined the presence and distribution of polycyclic aromatic hydrocarbons (PAH), other petroleum hydrocarbons (PHC) and phosphorus, derived from engine oil, in several Lake Tahoe soils and sediments. The PAH profile in marina sediments, road runoff locations and from water collected immediately after running a 4 stroke engine in a tank had similar signatures, and data collected in this study offered strong evidence that engine emissions were the primary source of these hydrocarbon contaminants in Lake Tahoe soils and sediments. Two PAH’s, fluoranthene and pyrene were observed at relatively high concentrations, and were signature compounds in the sediments. In addition, a strong and positive correlation existed for PAH and TPH in road runoff soils and marina sediments indicative of PAH related to vehicle emission.

Phosphorus is an additive to most 4-cycle engine oils and observed at a concentration of 700-1500 mg/L in new and used engine oils. Although this source of phosphorous is potentially significant for nutrient addition to Lake Tahoe, it comprises only a relatively small fraction in the soils and sediments, compared to natural concentrations. The Tahoe soils examined had a total phosphorus content of 500-1000 mg/kg and an available phosphorus content of 20-100 mg/kg.1 % of phosphorus content in the oil and a TPH content of 3000-5000 mg/kg in the highly vehicle affected areas, the phosphorus contribution from engine oil is only 3-S5mg/kg. Alternatively, the hydrocarbon contaminated sediments released more phosphorus into the water under anaerobic conditions and suggests that petroleum hydrocarbons can drive anaerobic processes that eventually will release phosphorus.

This is likely an issue in marina sediments, as well as flooded catchment basin sediments. il The three catchment basins examined in the Kings beach area appeared effective in retaining the contaminants. The inlets had high TPH, and PAH concentrations in comparison to the outlets and soil cores collected at different depths in each basin had hydrocarbon concentrations low in the native depths and high in the layer where sediment had accumulated. PAH leaching was evaluated in basin soils and the results indicated that only a small fraction (<0.1%) of PAH compounds would leach.

iii ACKNOWLEDGEMENTS I thank Dr. Glenn Miller, for giving me the opportunity to work in his lab and complete my degree. Appreciation is extended to all my committee members, Dr. Dale Johnson, Dr.

Jerry Qualls, Dr. John Sagebiel, and Dr. Mark Walker for all their input and for their valuable advice. Special thanks for my colleagues who held my hand and encouraged me to never give up and push forward.

Their words were “no pain no gain”. I thank the agencies that funded this project (Tahoe Regional Planning Agency and Lahontan water Quality Board) and to all those helping hands Janis Hall and Elizabeth Harris. Gratitude is extended to Dr. Sandra Carroll, Kendra Zamzow, Cindy Hoonhout, Jim Woodrow and Victoriya Lepak for help with the lab instruments.

My sincere appreciation to Mary Miller at Desert Research Institute (DRI) for analyzing total phosphorus in soil samples and to Dr. Rick Susfalk who is also at DRI for his valuable input related to phosphorus in Lake Tahoe soils. I thank my parents and brothers for their constant encouragement. At a very young age, they made me believe that education is important fora woman.

Above all, I thank God for the opportunity that was given me. IV TABLE OF CONTENTS CHAPTER 1: Polycyclic aromatic hydrocarbons profile and total petroleum hydrocarbon loading in Lake Tahoe sediments ADSUract. cece cece ee eeeeeeseeveeveuveuveuveueeueeuvaueaueveevnrvnrvnrvnrvnrenens ÍnffOUCfIOHT. cece cece cece eee ee eee eeteeteeteeteeteeteeteeteenees Materials and methodS.

cece eee e eee ng nh snes ss (a) Four stroke engine operation to examine PAH compounds from engine emissions In WAf€T. cà e ene ene (b) Road dust and marina sampling. (c) Sediment characterization and TOC analysIs. 10 (d) Total petroleum hydrocarbon determination.

10 (e) Polycyclic aromatic hydrocarbon determination. lãi Results and discussion 16 (a) The distribution of PAH and PHC in marina sediments and 16 along in the road runoff areaS. TPH 17 TPH vs. TOC 17 PAH vs.

TOC 18 (b) The concentration of PAH in different sieve size fractions in 25 both marinas and road runoff locaflOns. (c) PAH profile observed in engine emission and in marina 30 S320 2. EE EE EEE EEE EEE Ee (d) Road runoff and marina locations PAH profile. 35 Conclusion 39 Literature cited 41 CHAPTER 2: Polycyclic aromatic hydrocarbons and total petroleum 45 hydrocarbons in three Lake Tahoe catchment basins 0u iuynỚaỤẦỤp.

HH nh nha 47 Materials and methods. c2 nh key 49 (a) Sampling ÏOCatIO'S. ch ky 49 (b) Leaching experImert. EEE EEE EE eee 57 (d) Statistical anaÏVSIS.

cece cece ence nh kh 59 Results and đISCUSSIOT.c CS SH nh nena ena ng 60 (1) Sources of PAH and TPH to the Tahoe basin.c {cớ 75 (a) Concentrations of polycyclic aromatic hydrocarbons (PAH), 75 total petroleum hydrocarbon (TPH), and total organic carbon (TOC) content in the baSInS.ccccc sees eases (b) PAH compounds and TPH in different sieve fractions in Coon, 84 Salmon, and Hwy 28 basin. (IIT) Leaching of the PAH compounds in different depths. cece cece eeeceeecesesvesvesvesvesvesvesvesvesvesvesvesvesvesvesvenss 100 Literature CI{€C. eee eee eee eee eee tsetse eee tsetse teens 101 CHAPTER 3: Phosphorus in engine oil and its availability in soils 103 and sediments ADSUract.

cece cece cece ceeeseeveuveueeuveueeuueueeuueueeuvavvanvanvnnvanvanvannass 104 IntrOoductiOn. ccc cece cece cece cee eeeceeeeeceeeeeeeteeteeteeteeeeneentee eee 105 Materials and methodS. ng ng nh khu 110 (a) Available phosphorus and petroleum hydrocarbon in Lake 110 Tahoe soils and sedIimenfs. (b) Phosphorus content in new and used engine oIÌs.

112 (c) water extractable phosphorus in engine oIÏs. 112 (d) Release of available phosphorus in sediments and soils under 113 anaerobic and aerobic cOndItIO'S. Results and đISCUSSIOT. nh nh nha 115 (a) Phosphorus content in new and used engine oiÌs.

115 (b) Water extractable and available phosphorus in 4 stroke and 118 used engine OIÏÌS.‹ ene en nen en nh kh hy (c) Available phosphorus and petroleum hydrocarbon in soils and 122 S€dIIN€TIS. ence eee tees neta ene ene ng nh nh nh nen (d) Release of bioavailable phosphorus under anaerobic and 132 aerobic conditions in soils and sediments. eee e cece cece cece eee e eee ee eee seeeeeeeeeeeeeeeee sees 138 iirarix-0i 0. AI 140 CHAPTER 4: Summary and Conclusions 143 vil LIST OF TABLES CHAPTER 1 Page Table 1.1: Physical properties of the polycyclic aromatic hydrocarbon compounds analyzed in this study (obtained from Syracuse Research Corporation website: hf{p://€SC.

ng Hi nh tư Table 1.2: Location of the road runoff and marina samples.3: The quantification ion, confirmation ions, and retention 15 time for each PAHs.4: PAH concentration (ng/g) dry wt. basis and TPH 19 concentration (mg/kg) dry wt. basis in road runoff and marina locations in Lake Tahoe sediments .5: Percent total organic carbon as a result of total petroleum 20 hydrocarbon in road runoff and marina locations.6: Road runoff and marina TOC (%) and PAH (ng/g) dry 21 wt. basis COTC€HẨTAf{OTIS.c CC co Table 1.7: Particle size distribution and TOC content of selected 28 road runoff and marinaS.8: Mean and standard deviation of PAH compounds in 32 water from engine emission and sediments.9: PAH compounds in engine emission and marina 33 sediments normalized to fluoranthene and the ratio of normalized marina to engine wafer.10: MANOVA showing the differences in PAH compounds 38 in road runoff and marina sediments when they were normalized to fluoranthene.

Vill CHAPTER 2 Table 2.1: Less vehicle affected sampling locations in Kings 50 ; u00. eee ee ener .2: Highly vehicle affected sampling location in Kings 51 Beach. cece cc eceeeeceee ences ee eeeeneeneeeeneeneenenens Table 2.3: Soil types in the Kings Beach.4: Depths used for each basin for statistical analysis.5: Concentrations of total petroleum hydrocarbon (TPH) 62 mg/kg dry wt. basis and polycyclic aromatic hydrocarbons (PAH) ng/g dry wt.

basis for sites less affected by vehicle traŸllc.6: Concentrations of total petroleum hydrocarbon (TPH) 63 mg/kg dry wt. basis and polycyclic aromatic hydrocarbons (PAH) ng/g dry wt. basis for sites affected by vehicle trafflc.7: PAH, TPH, and TOC content of Coon basin.8: PAH, TPH, and TOC content of Salmon basin.9: PAH, TPH, and TOC content of Hwy 28 basin.10: | PAH concentrations (ng/g) dry wt. basis at different 78 depths in Coon basin.11: | PAH concentrations (ng/g) dry wt.

basis at different 78 depths in Salmon basin.12: | PAH concentrations (ng/g) dry wt. basis at different 79 depths in Hwy 28 basin.cc ene ee 1X Table 2.13: Statistical significance of PAH, TPH, and TOC for the 83 three basins at the three selected depths.14 Coon basin percent distribution of sediments in sieve 85 sizes at the different depths.15: Salmon basin percent distribution of sediments in 85 different sieves at the different depths.16: Hwy 28 basin percent distribution of sediments in 86 different sieves at the different depths.17: Leachate results of the Coon basin at 14cm depth.18: Leachate results of the Coon basin at 20cm depth (n=3).19: Leachate results of the Salmon basin at 14cm depth (n=3) 94 Table 2.20: Leachate results of the Salmon basin at 20cm depth (n=3) 95 Table 2.21: Leachate results of the Hwy 28 basin at 12cm depth 97 Table 2.22: Leachate results of the Hwy 28 basin at 20cm depth 98 Cle) re CHAPTER 3 Table 3.1: Annual phosphorus loading budget for Lake Tahoe from 106 Reuter et al. ccc ee ccce ch nhau Table 3.2: Percent total organic carbon (TOC) and total petroleum 115 hydrocarbon (TPH) of soils from three depths in catchment basins and marina sediments Table 3.3 Concentrations of elements (mg/L) found in 2 stroke 117 engine oils, 4 stroke engine oils and used oils (analyzed by Stavely Fluid analysis services, Sparks, NV).4: Extractable total phosphorus and available phosphorus 120 from I ml of new and used oils into wafer.5: Extractable total and available phosphorus in 49 ml of 121 water (mg/L) when Iml of the following new and used Oils Were MIXEd. cece eet e eee eee ene Table 3.6: Total petroleum hydrocarbon and bioavailable 126 phosphorus from areas affected by less vehicle traffic in Kings Beach.

eee ee eee eee nena een es Table 3.7: Total petroleum hydrocarbon and bioavailable 127 phosphorus from highly vehicle traveled areas .8: Total petroleum hydrocarbon, TOC content, and 128 bioavailable phosphorus of the marina sediments in mg/kg dry wt basis and percentage (1%=10,000 ppm) .9: Percent of bioavailable phosphorus as a result of engine 129 oil in less vehicle affected sites, sites highly affected by vehicle activity, and marInaS.10: Eh readings of anaerobic and aerobic sediments and 134 Table 3.