Examination of Metals from Aerospace-Related Activity in Surface

Apr 8, 2014 - National Institute of Standards and Technology (NIST), Hollings Marine ... Marine Biomedicine and Environmental Sciences, Medical Univer...
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Examination of Metals from Aerospace-Related Activity in Surface Water Samples from Sites Surrounding the Kennedy Space Center (KSC), Florida John A. Bowden,*,† Theresa M. Cantu,‡ Douglas M. Scheidt,§ Russell H. Lowers,§ Brian A. Nocito,∥ Vaneica Y. Young,∥ and Louis J. Guillette, Jr.‡ †

National Institute of Standards and Technology (NIST), Hollings Marine Laboratory, Charleston, South Carolina 29412, United States ‡ Department of Obstetrics and Gynecology and Marine Biomedicine and Environmental Sciences, Medical University of South Carolina (MUSC) and the Hollings Marine Laboratory (HML), Charleston, South Carolina 29425-6190, United States § InoMedic Health Applications (IHA), Ecological Program, IHA 300, Kennedy Space Center, Florida 32899, United States ∥ Department of Chemistry, University of Florida (UF), Gainesville, Florida 32611, United States S Supporting Information *

ABSTRACT: Metal contamination from Space Shuttle launch activity was examined using inductively coupled plasma-atomic emission spectroscopy in a two-tier study sampling surface water collected from several sites at the Kennedy Space Center (KSC) and associated Merritt Island National Wildlife Refuge in east central Florida. The primary study examined both temporal changes in baseline metal concentrations (19 metals) in surface water (1996 to 2009, 11 sites) samples collected at specific long-term monitoring sites and metal deposition directly associated with Space Shuttle launch activity at two Launch Complexes (LC39A and LC39B). A secondary study examined metal concentrations at additional sites and increased the amount of elements measured to 48 elements. Our examination places a heavy focus on those metals commonly associated with launch operations (e.g., Al, Fe, Mn, and Zn), but a brief discussion of other metals (As, Cu, Mo, Ni, and Pb) is also included. While no observable accumulation of metals occurred during the time period of the study, the data obtained postlaunch demonstrated a dramatic increase for Al, Fe, Mn, and Zn. Comparing overall trends between the primary and secondary baseline surface water concentrations, elevated concentrations were generally observed at sampling stations located near the launch complexes and from sites isolated from major water systems. While there could be several natural and anthropogenic sources for metal deposition at KSC, the data in this report indicate that shuttle launch events are a significant source.

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INTRODUCTION

One transient activity that has recently garnered attention is fireworks displays. The toxicity of emissions from this activity can generally be contributed to two factors: particle size (respirable particulate matter vs larger particles,14) and the chemical toxicity of the emissions, which include organic compounds,15 perchlorate,16 metalloids (trace additives for coloring purposes17), and metals.18 In particular, fireworks displays have been shown to disperse significant amounts of metal waste (ten to thousand-fold increases) into the surrounding environment in a short period of time.19−23 In addition to metal waste, firework displays have also been shown

Although several metals have been deemed essential for biological purposes, there is increasing evidence that elevated exposure to specific metals can be detrimental to the environment and human health.1−5 In general, the occurrence of metals in the environment originates from several natural sources, including contributions from seawater,6,7 geological deposits, 8 and other elemental cycles.9,10 Despite the ubiquitous nature of metals, there is a heightened awareness of widespread deposition and accumulation of metals in the biosphere as a result of anthropogenic activity.11−13 To further improve the total assessment of anthropogenic pollution in both local and global environments, new studies should focus on expanding the range of anthropogenic practices monitored, particularly characterizing the metal waste derived from atypical and lesser-studied anthropogenic activities. © 2014 American Chemical Society

Received: Revised: Accepted: Published: 4672

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Figure 1. (A) An overall site map (left figure) of the environment surrounding the Kennedy Space Center (KSC). The 11 LTM baseline sampling stations for surface water from the primary study are shown as sites A−K. The sites are described in terms of the location as follows: A = LC39A, B = LC39B, C = inlet of Banana Creek, D = southwest shoreline of Banana River South, E = northeast Banana River, F = southeast shoreline of Banana River, G = lower Mosquito Lagoon, H = southern terminus of Max Hoeck Creek, I = near LC39B, J = northwest Banana River, and K = middle Banana River. Baseline surface water, as part of the secondary study, are shown as sites 1−14. The pre and postlaunch samples for both studies were collected within immediate proximity (north) to LC39A (A, 6) and LC39B (B), respectively. Three sites were the same between the primary and secondary study (6 = A, 7 = E, 8 = C) and were used for comparison purposes. Sites A/6, J, 3, and 5 are located in the enhanced map for LC39A (top right), while sites B, I, and 4 are located in the enhanced map for LC39B (bottom right).

Refuge (MINWR) and Canaveral National Seashore, within KSC property, increases the need to monitor and understand metal deposition into the environment from anthropogenic contributions. Using inductively coupled plasma−atomic emission spectroscopy (ICP-AES), metal deposition originating from anthropogenic activity was characterized in a two-tier study by examining environmental samples collected from several sampling sites on KSC. The primary study aimed to examine 19 metals in baseline and pre/post shuttle launch surface water samples from 1996−2009. A survey of the changes in metal distribution postlaunch were obtained for 25 (launch complex (LC), LC39A) and 16 (LC39B) shuttle launches. To complement the primary study, an independent secondary study was performed in parallel (2009), in an effort to (1) obtain elemental concentrations at additional sites not included in primary study; (2) to increase the number of elements surveyed (from 19 to 48); and (3) to allow a comparison to confirm the measurements made in the primary study (at similar sites). While a large focus of this investigation was to examine the potential deposition of metals implicated with shuttle launch operations (i.e., Al, Fe, and Zn),35,38,39 the incidence of other metals is also described. In addition, commentary is provided qualifying the presence and temporal burden of metals at KSC, as well as proposing future strategies to assess the impact on the biosphere.

to produce substantial increases in harmful gases and inhalable particulate matter.24,25 To provide specific combustive and coloring properties, specific metals, such as Al, Ba, Ca, Fe, and Mg, are added to fireworks in varying amounts.22,26 Similarly, the chemical properties (e.g., combustibility, durability, and machinability) of several metals have been exploited by the aerospace industry.27−29 Alloys, made from both common and rare-earth metals, have been heavily utilized in the engineering of spacecraft engines, semiconductors, and other specialized aerospace-components.27,30,31 In addition, metals have been used as integral components of solid rocket fuel.32 For each shuttle launch, approximately 450 000 kg of particulate matter is generated from the operation of solid rocket booster motors, as well as other material, such as paint chips and other ablated matter.33,34 This material, which is fundamentally composed of metals, such as Al (rocket fuel), Fe (catalyst in fuel), and Zn (zinc oxide coating on launch pad to prevent corrosion),35 along with ammonium perchlorate (which is the primary source of hydrochloric acid, HCl), has the potential of being deposited directly into the environment surrounding the launch pads, as well as into the atmosphere for possible later deposition. Thus, although ephemeral in nature, aerospace-related activities possess the potential of contributing significant levels of metal waste into the environment, especially the “near environment” regions associated with these activities. Since 1960, the Kennedy Space Center (KSC), located at Cape Canaveral, Florida, U.S.A., has been a principal site for aerospace-related activities, including Space Shuttle operations.36,37 The presence of the Merritt Island National Wildlife

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EXPERIMENTAL SECTION Primary Study. Baseline Monitoring of Metals in Surface Water Samples Collected from 11 LTM Sampling Stations

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Figure 2. Primary study: pre- and postlaunch metal concentrations (in mg/L) at sites LC39A and LC39B for (A) aluminum, (B) iron, (C) manganese, and (D) zinc. 4674

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was created by diluting the tuning solution to final concentration values of 0.01, 0.05, 0.1, 0.2, 0.5, 1.0, 2.0, and 10 mg/mL. For the three metals that were detected in the environmental samples above the standard calibration curve (Ca, Mg, and Na), additional standards of 25, 100, and 200 mg mL−1 (from stock quantities of chlorinated salts) were added to extend the linear dynamic range. A matrix-matched blank was prepared by adding concentrated nitric acid to deionized water to a final concentration of 2% (12M, Fisher Scientific, Fair Lawn, NJ). The average baseline metal concentration (in mg/ L) and standard deviations for each metal at each site are shown in SI Table S9. The calibration standards (N = 3 for each standard) were analyzed three times at each target wavelength. The target wavelengths chosen (SI Table S8) for each element were based on a combination of factors, specifically those previously employed in a method developed by the EPA (200.7)41 and those which had primary or secondary emission lines which minimized potential spectral interferences observed in preliminary experiments. The intensities at each wavelength were recorded (after blank correction) using a Varian Vista ICP-AES instrument. The Vista software was configured to employ the simultaneous equation method to determine the elemental concentrations while minimizing the interferences from other elements. The corrected intensities, combined with statistical regression, were used to establish the linear dynamic range (LDR) for each element. In several cases, the concentrations of Ca, K, Mg, and Na in the environmental samples were estimated by extrapolating beyond the calibration curve. The linear range, relative standard deviation (RSD), limit of detection (LOD > 3σ, where σ is the standard deviation of the matrix-matched blank) and limit of quantification (LOQ > 10σ) were determined for each metal that was detected in the surface water samples, as shown in SI Table S8. The ICP-AES instrument was configured in a radial position using a power setting of 1 kW. The plasma, auxiliary, and nebulizing flows were set at 15, 1.5, and 1.5 L min−1, respectively. Argon (with purity of 99.5%) was used as the nebulizer gas. Pre- and Postshuttle Launch Metal Concentrations in Surface Water Samples Collected from Launch STS-127 at LC39A in 2009. Pre- and postlaunch water samples for the secondary study were performed in accordance with the baseline measurements. Surface water samples were collected at site 6 (as shown in Figure 1) several weeks prior to (on 6/ 10/2009 at 10:20 am) and approximately 15 hours postshuttle launch (on 7/16/2009 at 9:20 am). The Space Shuttle Endeavor STS-127 launched from LC39A on 7/15/2009 at 6:03 pm. The previous launch from LC39A occurred on 5/11/ 2009 at 2:01 pm. The surface water samples (N = 3) were collected and stored as previously described. The pre- and postlaunch metal concentration values for Al, Ca, Fe, Ga, K, La, Mg, Mn, Na, Sr, V, and Zn are shown in Figure 3.

from 1996 to 2009. Baseline surface water samples were repeatedly collected from 11 primary long-term monitoring (LTM) sampling stations (sites A−K, Figure 1), that included both launch complexes LC39A (site A) and LC39B (site B). Additional information on site location and selection can be found in the Supporting Information, SI. Baseline measurements were collected quarterly from 1996 to 2003 and biannually from 2003 to 2009, on average, over the time period of the study (sampling dates for each measurement for each sampling station are listed in Tables S1 and S2 in the SI). Each water sample (N = 1) was processed and analyzed (by multiple NASA-contracted laboratories) for Ag, Al, As, Be, Cd, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, Pb, Sb, Si, and Zn according to the United States (U.S.) Environmental Protection Agency (EPA) method 6010c.40 The average baseline metal concentration (in mg/L), standard deviation, and sample hits (the number of times the metal was detected divided by the total number of sample determinations) are shown in SI Table S3. The baseline samples were collected and measured at time intervals with no regard for time duration prior to or after shuttle launches. Average water measurements (pH and salinity) for each site over the time frame of the study, including Space Shuttle launches at LC39A and 39B, were collected using standard analogue and digital water quality instruments appropriate and available at the time and are shown in SI Table S4. Pre- and postlaunch monitoring of metals in surface water samples collected from LC39A and LC39B from 1996 to 2009. Pre- and postlaunch surface water samples were analyzed in accordance with the same procedures employed for the baseline measurements (N = 1 for each launch). Pre- and postlaunch collection and analysis dates for each sample obtained from LC39A and LC39B are shown in SI Tables S5 and S6, respectively. For sample collection, surface water samples were collected in a plot, 400 m directly behind each launch complex in line with the flame trench. Prelaunch surface water samples were typically collected several days prior to launch (most 1 mg/L) with metal salts of Ca, K, Mg, Na, and Sr, although most of the other metal salts (Al, Fe, Ga, La, Mn, V, and Zn) exist at much lower levels ( site C (as shown in SI Table S10), which demonstrated that sediment concentrations were elevated at the launch complexes in comparison to a site distanced from the launch pads (site C), although site C could have contributions from other anthropogenic activity. Other techniques, such as sediment coring or implementation of sediment containment structures (to prevent resuspension), should be explored in future analyses to improve the assessment of long-term metal deposition. Metal Influx in the Environment. The relationship between a Space Shuttle launch and its corresponding metal deposition has predominantly focused on examining the massive exhaust plume generated during the launch event. Typically, the solid rocket fuel is made up of aluminum powder (fuel), iron oxide (catalyst), ammonium perchlorate (oxidizer), and a polymer binder.32,44 Postshuttle launch, the resultant exhaust plume has been shown to disperse several byproducts, most notably several gases (e.g., gaseous hydrogen chloride) and aluminum oxide (Al2O3).45−47 The amount of hydrogen chloride (or HCl upon hydration with water) and aluminum oxide generated from a shuttle launch can reach up to several thousand kilograms (in a 1 km2 area), prompting several studies to examine its potential negative effect on the ecosystem at MINWR.48−53 As a result of the high levels of HCl deposited into the local environment (mixing with over 190 000 L of water from exhaust), pH levels drop dramatically, with a concomitant increase in salinity (on average about 2 g/L). Postshuttle launch, the pH in water near launch pads has been recorded as low as 1.5 immediately following a launch.34,54 Although the average measured pH level of the postlaunch surface water in this study was 6.13 (from 8.13 prelaunch for LC39A), 5.97 (from 8.40 prelaunch for LC39B), and 6.06 (down from 7.85 prelaunch), for the primary and secondary study (as shown in SI Tables S4 and S7), respectively; the pH value was most likely considerably lower immediately after the launch, as it has been reported that the neutralizing capabilities of the ecosystem surrounding LC39A can rebound the pH

more likely the result of anthropogenic deposition rather than from coastal influences. Primary Study: Discussion of Pre- And Postshuttle Launch Metal Concentrations in Surface Water and Comparison to Baseline Measurements. The measurements for LC39A and LC39B represented 25 and 16 shuttle launch events, respectively, over the time period (as shown in SI Tables S5 and S6). Of the 19 elements (Na not included), only Al, Fe, Mn, and Zn exhibited a significant increase postshuttle launch (for both LC39A and LC39B), as shown in Figure 2A−D. For these metals at LC39A, there was an approximate percent increase in metal concentration (%) of 300, 500, 140, and 2900 for Al, Fe, Mn, and Zn, respectively, postshuttle launch (in comparison to prelaunch concentrations). Further, for LC39B, there was an approximate percent increase in metal concentration (%) of 1000, 5400, 900, and 4800 for Al, Fe, Mn and Zn, respectively, postshuttle launch (in comparison to prelaunch concentrations). For comparison, K and Mg are shown in SI Figures S1 and S2, and exhibit no significant difference between pre- and postshuttle launch measurements. In addition, the postshuttle launch concentrations were significantly higher than the average baseline concentrations previously described, further substantiating the deposition of metals by anthropogenic practices. It should be noted that the concentration value postshuttle launch was directly impacted by the time the samples were collected postlaunch, as those measurements taken from samples collected >1 day after launch (STS-90, 99, 95, 110, 116, and Ares-1X) generally had reduced increases in comparison to those measurements taken 1 day postlaunch). Several reports have demonstrated that lower pH values lead to an increase in metal availability55−57 and thus potentially an increase in metal uptake by the surrounding wildlife, often leading to an increased toxicity to plants, invertebrates, fish, and higher predators.5,58−62 Toxicity can result through multiple mechanisms, among which include mimicry (with essential metals), interference with binding actions (i.e., proteins), disruption of normal cell signaling, and the promotion of oxidative stress.1,63 In addition, several metals have the potential to accumulate through various food webs, and subsequently bioaccumulate in top predators, as shown in biological samples obtained from several wildlife species, thus resulting in an increased exposure level.64−66 Few studies have examined the health impact of metal contamination on wildlife species at MINWR. A recent study done by Horai et al.67 reported a correlation of several metals found in both juvenile and adult America alligators to those commonly used in aerospace-related activities, with some noted to accumulate with age. Further, it was shown that adult alligators had Fe levels above what is considered toxic in other species.67 It should be noted that determining toxicity in a potentially contaminated environment, such as MINWR, is a complicated task, highlighted by issues stemming from (1) a long history of exposure (separating long-term vs short-term effects), (2) understanding the basal levels per species (to determine normal vs toxic levels), (3) knowing what species-specific metabolic end points/patterns are associated with toxicity, (4) understanding the synergetic toxicity of unknown mixtures of metals and organic contaminants, and (5) confounders to toxicity, such as age, size, sex, and season. Thus, more work needs to be performed to assess not only the source of metal deposition, but also the mechanism by which it is dispersed and the impact of this dispersion on the biosphere. The most straightforward explanation for the presence of metals (Al, Fe, Mn, and Zn) in surface water postlaunch can be explained through deposition from the rocket exhaust plume; however, it is also possible that the elevated surface water concentrations are due to an influx of metals from sediment (as supported by the fact that baseline sediment metal concentrations were elevated around the launch pads). Shuttle launches are turbulent events and can disturb sediment (especially in shallow Florida water systems68), leading to a temporary influx of sediment material into the surface water. This aspect, in combination with a low pH immediately following a shuttle launch (from introduction of HCl), could also explain the elevated metal concentrations post launch. Thus, the concentrations of metals in surface water postshuttle launch likely are a combination of both deposition from the exhaust plume and reincorporation of material from the sediment.

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ASSOCIATED CONTENT

S Supporting Information *

Additional information regarding the sites selected, as well as the baseline metal concentrations in surface water (for the primary and secondary studies) and sediment samples (for primary study), sample collection dates, and water properties. In addition, details regarding the Space Shuttle launches are also provided. This material is available free of charge via the Internet at http://pubs.acs.org/.

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AUTHOR INFORMATION

Corresponding Author

*Phone: 843-762-8960; e-mail: [email protected]. Notes

Disclaimer. Certain commercial equipment, instruments, or materials are identified in this paper to specify adequately the experimental procedure. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology; nor does it imply that the materials or equipment identified are necessarily the best for the purpose. The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors would like to thank Burt Summerfield, Lynne Phillips, John Shaffer and staff of the Ecological Program at the NASA Kennedy Space Center for use of existing data and for permission to collect and analyze the environmental samples from the area inside the security boundary. Over the years many people helped with field collections: Carlton Hall, Mark Provancha, Jane Provancha, Mario Mota, Eric Reyier, Karen Holloway-Adkins, Shanon Gann and Carla Garreau.

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REFERENCES

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