Science of the Total Environment 472 (2014) 9–12
Contents lists available at ScienceDirect
Science of the Total Environment journal homepage: www.elsevier.com/locate/scitotenv
Short Communication
Pilot survey of methamphetamine in sewers using a Polar Organic Chemical Integrative Sampler Tammy H. Boles a,1, Martha J.M. Wells a,b,⁎,2 a b
Department of Chemistry, Tennessee Technological University, Cookeville, TN 38505, USA Center for the Management, Utilization and Protection of Water Resources, Tennessee Technological University, Cookeville, TN 38505, USA
H I G H L I G H T S
G R A P H I C A L
A B S T R A C T
• Polar Organic Chemical Integrative Samplers (POCIS) were deployed into sewer lines. • Proof-of-concept was established for using POCIS devices in the sewage system. • POCIS sorbent extracts were analyzed via HPLC–MS/MS. • Methamphetamine was detected within the sewage collection system. • The data encourage research for future use as a forensic tool in law enforcement.
a r t i c l e
i n f o
Article history: Received 4 July 2013 Received in revised form 31 October 2013 Accepted 31 October 2013 Available online xxxx Keywords: Methamphetamine Passive sampler Sewer Forensic Wastewater
a b s t r a c t A pilot study for the qualitative detection of methamphetamine at sites within a sewage collection system adjacent to locations suspected to harbor illegal drug activities was investigated and preliminary findings are reported. Sewage samples were collected over a time interval of four weeks using a Polar Organic Chemical Integrative Sampler (POCIS) deployed directly into the sewer line. The POCIS sorbent was extracted and analyzed via high-performance liquid chromatography tandem mass spectrometry (HPLC–MS/MS). Methamphetamine was found in sewage from one of three sampling sites at a concentration greater than the HPLC–MS/MS method detection limit (MDL) of 3 ng/mL. The goal of this research was to establish proof-of-concept of the feasibility for sampling and analysis using POCIS devices in the sewage collection system. The data encourage further testing and research. The ability to pinpoint the presence of methamphetamine in the sewer may in the future be used as a forensic tool in law enforcement. © 2013 Elsevier B.V. All rights reserved.
1. Introduction
⁎ Corresponding author. E-mail addresses: [email protected] (T.H. Boles), [email protected], [email protected] (M.J.M. Wells). 1 Present address: School of Environmental Studies, Tennessee Technological University, Cookeville, TN 38505, USA. 2 Present address: EnviroChem Services, 224 Windsor Drive, Cookeville, TN 38506, USA. 0048-9697/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.scitotenv.2013.10.122
Methamphetamine — also known as “meth,” “speed,” and “crank,” — is a highly addictive, powerful nervous system stimulant. Because methamphetamine is so addictive, it is illegal to manufacture or use methamphetamine, except by prescription, under U.S. Federal Law. In the United States, the Drug Enforcement Administration (DEA) classified methamphetamine as a Schedule II substance, available only by prescription but
10
T.H. Boles, M.J.M. Wells / Science of the Total Environment 472 (2014) 9–12
rarely prescribed (DEA Fact Sheet: Methamphetamine, 2013). Methamphetamine is illegally sold in pill, capsule, powder, and chunk form. In its pure form, the hydrochloride salt of methamphetamine is yellow to colorless, although the street drug may be colored due to impurities. The drug can be created cheaply and easily in clandestine, “clan,” labs and can be smoked, snorted, inhaled, or injected. Because methamphetamine is so cheap and easy to produce, clandestine labs have proliferated and have been found in all states of the United States. In 1993, DEA officials estimated that 218 labs existed; in 2004 almost 15,000 labs were seized (109th Congress Report, House of Representatives, 2013). In Tennessee, USA, law enforcement agencies across the state have encountered approximately 7600 clandestine methamphetamine labs from 1998 to present (Cleanup of Methamphetamine Contaminated Properties, 2013). Illicit drugs, such as methamphetamine, can enter source waters through wastewater treatment plant effluents (i.e., human excretion), and via manufacturing in clandestine laboratories (USEPA, 2008). Pharmaceutical and personal care products (PPCPs) in the environment are not regulated in the United States but enter the urban water cycle and have the potential to negatively affect water quality. Upon contamination of a water source, methamphetamine produced in a clandestine laboratory cannot be distinguished from methamphetamine consumed and excreted by humans. Based on published reviews from both the United States and Europe (Vazquez-Roig et al., 2013; Zuccato and Castiglioni, 2009, 2011; Kasprzyk-Hordern, 2011; van Nuijs et al., 2011; Castiglioni and Zuccato, 2010; Boles and Wells, 2010; Castiglioni et al., 2008), measurable concentrations of amphetamine and methamphetamine — two of a class of drugs known as amphetamine-type stimulants (ATSs) — have been found in wastewater, biosolids, surface water, and sediment. Local news reports have chronicled several instances of clandestine methamphetamine laboratories and arrests for methamphetamine possession and abuse, lending credence to the hypothesis that it would be found in wastewater. However, no previous studies have been conducted to detect the presence of methamphetamine directly from sewer pipes. Wastewater and surface water samples for research are generally collected through traditional water sampling techniques, such as grab sampling or composite water sampling. A grab sample is collected simultaneously in its entirety and reflects a single data point in time, while a composite sample involves collecting discrete samples taken at specific intervals of time and combining them at the end of the sampling period into a single sample. The composite sample reflects an average concentration of the analyte in the water source over the sampling time period. However, grab samples, and even composite samples, only capture information at that moment or over a specified short sampling period. In addition, grab and composite sampling techniques may miss important events, such as high or low flow, precipitation, and variability in chemical loading. As an alternative, passive sampling devices are being used to monitor hydrophilic/hydrophobic contaminants such as pesticides, PPCPs, and illicit drugs in aqueous environments, and are designed to stay in the aqueous environment for several days, weeks, or even months (Harman et al., 2012). The Polar Organic Chemical Integrative Sampler (POCIS) device combines the ability to integrate exposure over time during a range of hydrologic conditions with the ability to accumulate a detectable mass of a compound that may be present in a water sample at concentrations below the method detection level (Alvarez et al., 2005). The design of the POCIS device allows it to mimic the exposure of the respiratory system of aquatic organisms to dissolved chemicals (Alvarez et al., 2004). POCIS samplers have been employed for quantitative identification of numerous wastewater-related contaminants, including methamphetamine in surface water (Jones-Lepp et al., 2012; Bartelt-Hunt et al., 2009), sediment (Alvarez et al., 2012), and wastewater (Harman et al., 2011; Bartelt-Hunt et al., 2009; Jones-Lepp et al., 2004). POCIS sampling rates (a value needed for quantitative backcalculation of environmental concentrations) have been determined
for some compounds, including methamphetamine (Bartelt-Hunt et al., 2009, 2011; Harman et al., 2011; Alvarez et al., 2007). However, even though the membrane in POCIS devices is not as subject to biofouling as other membrane types (Alvarez et al., 2004), biofouling can still occur, causing uptake kinetics and subsequently, laboratory-derived calibration data to be modified (Mills et al., 2007). The goal of this research was to establish a proof-of-concept regarding the feasibility for sampling and analysis in the sewage collection system and to provide a qualitative assessment of the occurrence of methamphetamine using POCIS, because raw sewage near the source is not as dilute as wastewater influent, and is more likely to cause biofouling of the POCIS device. Therefore, the research reported in this paper focuses on the preliminary findings from a pilot study that used POCIS devices to monitor raw sewage for methamphetamine in the sewage collection system before the raw sewage reaches a wastewater treatment plant. The ability to pinpoint the location of methamphetamine in the sewer may at some time in the future be used as a forensic tool in law enforcement. 2. Material and methods 2.1. POCIS deployment and sampling Sampling occurred at sites in Cookeville, TN, USA that were known hotspots for drug activity because information about methamphetamine-related arrests is published regularly in the local newspaper. POCIS devices were deployed in three different sewer lines originating from three buildings suspected to harbor illegal drug activities. For privacy purposes, the sites will be referred to as Site 1, Site 2, and Site 3. Although deployment canisters can be used to house the devices, the small size of the sewer pipes tested in this research prevented the use of canisters, such that two devices were held together with a plastic zip tie and were placed inside city-owned sewer lines at the junction between the private sewer line and the city-owned line. The samplers were deployed for a total sampling period of 27 days. 2.2. POCIS characteristics AQUASENSE-P POCIS devices were obtained from Environmental Sampling Technologies (St. Joseph, MO) as based on a patented design (Petty et al., 2002) consisting of 200 mg of Oasis hydrophilic-lipophilic balanced (HLB) sorbent contained between two membranes made of hydrophilic polyethersulfone (PES) with a 0.1 μm pore size and a 41 cm2 surface area. Upper and lower stainless steel support rings are used to seal the device and prevent loss of sorbent. Although two POCIS devices were used for sampling each site, the devices were extracted separately. Extraction of the POCIS devices and HPLC–MS/MS analysis for methamphetamine are described in supplementary data associated with this manuscript. 3. Results and discussion 3.1. Pilot monitoring using POCIS devices The POCIS device configuration used in this research consisted of 200 mg of Oasis HLB sorbent sandwiched between PES membranes with a surface area of 41 cm2 as purchased from the manufacturer. This construction meets standardized surface area to sorbent/lipid volume (SA/V) specifications described by Alvarez et al. (2007, 2012). Pharmaceutical POCIS devices are designed to be appropriate for most pharmaceuticals and contain only HLB sorbent, as opposed to the pesticide POCIS devices that contain three different sorbents and target pesticides as well as hormones and wastewater treatment chemicals. HLB sorbents are made by polymerizing divinylbenzene (lipophilic) and N-vinylpyrrolidine (hydrophilic) monomers. They are capable of extracting acidic, basic and neutral analytes, which may be polar or
T.H. Boles, M.J.M. Wells / Science of the Total Environment 472 (2014) 9–12
nonpolar. Methamphetamine — a weak base — is a 2° amine with a pKa = 10.38. No sorbents other than HLB were tested in this research. In late summer, two POCIS devices each were deployed in sewer lines originating from three buildings suspected to harbor illegal drug activities referred to as Site 1, Site 2, and Site 3. The devices were placed inside city-owned sewer lines at the junction between the private sewer line and the city-owned line. The samplers were retrieved after a total sampling time of 27 days (Petty et al., 2002). POCIS devices from Site 1 (Fig. 1) and Site 2 were extremely dirty with a visible accumulation of slime on the PES membrane. One of the POCIS devices from Site 1 had a puncture through one side of the membrane. POCIS devices from Site 3 were only slightly soiled. Analysis of the sample from Site 1 was positive for the presence of methamphetamine (see Supplementary data). The data support the conclusion that methamphetamine was present in the sewer line from Site 1 and that, qualitatively, it was present at concentrations greater than the method detection limit (MDL) of 3 ng/mL. The sample extract from Site 2 was not positive for methamphetamine. Site 3 POCIS devices were only slightly dirty; the sorbent was not discolored and did not appear to have been wetted. The appearance of the device and sorbent suggest minimal, if any, sewage flow across the device. At Site 3, the POCIS device may have been improperly positioned or no sewage flowed across the POCIS device during the time it was deployed. 3.2. Qualitative versus quantitative measurement of target analyte concentration In other studies, POCIS devices have been employed for quantitative identification of environmental concentrations of methamphetamine in surface water (Jones-Lepp et al., 2012; Bartelt-Hunt et al., 2009), sediment (Alvarez et al., 2012), and wastewater (Harman et al., 2011; Bartelt-Hunt et al., 2009; Jones-Lepp et al., 2004). However, in this research, due to the nature of the sewer line sites sampled, qualitative
11
assessment only of the presence or absence of methamphetamine above a threshold level was appropriate for POCIS deployment in the sewer system and adequate to meet the goals of this project. In situ quantitative application of POCIS data for the assessment of environmental concentrations is based on certain assumptions: the POCIS device is submerged during the entire deployment period, the average flow rate during the length of deployment is known, the turbulence or lack thereof for the site is known, sorption of the analyte is based upon linear uptake rate kinetics, fluctuations in temperature are small, and biofouling is minimal. For complete quantitative calculation of analyte concentration after environmental exposure of a POCIS device, the content of the POCIS sorbent is analyzed and that data is used to back-calculate a time-weighted average concentration at the site deployed based on (1) the uptake rate of the specific analyte and (2) the flow rate of the environmental compartment (Alvarez et al., 2007). The uptake or sampling rate for methamphetamine on standard POCIS devices has been determined and reported (Bartelt-Hunt et al., 2009, 2011; Harman et al., 2011; Alvarez et al., 2007) based on calculation (Bartelt-Hunt et al., 2009), laboratory calibration (Bartelt-Hunt et al., 2011; Alvarez et al., 2007), or field-deployed environmental conditions (Harman et al., 2011). However, the sampling rate for methamphetamine is not established for a sewer line. The stability of methamphetamine during the sampling time is not known—the extent to which methamphetamine is degraded after sorption is uncertain. However, if methamphetamine were present on the sorbent but degraded below the detection limit during deployment, a false negative result would be reported. Additionally, the average flow rate of the environmental compartment is indeterminate for sampling in a sewer line compared to surface water or wastewater field sites. The average flow rate in the sewer lines sampled in this research could have varied substantially during the deployment of the device. The device may not have been submerged during the entire deployment period, and it may be envisioned that conditions during deployment varied between quiescent and turbulent flows in the sewer line. For these reasons, qualitative assessment of the presence or absence of the target analytes is presented here rather than complete quantitative determination. Because the fundamental assumptions regarding deployment were not established and the potential degradation of the analyte is unknown, back-calculation to determine the concentration during deployment was not conducted and qualitative assessment only of the sampling results is reported. In the future, issues of flow rate, submersion, and turbulence in the sewer lines may be determined to render it possible to quantitatively calculate time-weighted average concentrations. Meanwhile, qualitative application, as in this research, is shown to be feasible. Analytically, it is not possible to distinguish the methamphetamine originating from human excrement from that produced in an illegal laboratory. Characteristic synthetic precursors and by-products of methamphetamine manufacturing could additionally be monitored in the future to verify the presence of a clandestine laboratory. However, the proof-ofconcept of the deployment of POCIS devices as qualitative samplers indicating the presence/absence of an analyte-of-interest in sewer lines was demonstrated. 3.3. Ethical and legal aspects of this study
Fig. 1. POCIS devices after deployment in sewer lines for one month and initial external cleaning.
As in this report, scientific advancement often outpaces associated ethical and legal questions. Herein, a new scientific approach to monitoring the presence/absence of an illegal chemical substance within the sewage distribution system prior to reaching its destination in a municipal sewage treatment plant is reported. The methodologies employed here were determined to be scientifically feasible, but questions can be raised as to the ensuing ethical and legal aspects of this study. In summary, sampling occurred in municipal areas near commercial buildings that were known hotspots for illegal drug activity because information about arrests is published in the local newspaper. No individual
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T.H. Boles, M.J.M. Wells / Science of the Total Environment 472 (2014) 9–12
households were targeted in this research. For privacy purposes, no maps or other identifying information was provided in this manuscript—sites were referred to as Site 1, Site 2, and Site 3. Devices were placed inside city-owned sewer lines at the junction between private and city-owned sewer lines. At no time were private property sewer lines breached. Permission to deploy the POCIS devices was granted by the municipal sewerage company. Wastewater treatment plant sampling (influent and effluent) is reported with frequency in the literature. However, this research raises ethical questions regarding privacy and targeting sources when sampling upstream of the wastewater treatment plant, and should promote discussion of these matters. The data collected in this pilot study was intended only to establish the scientific feasibility of this application, and was not used in a legal case. The ability to pinpoint the location of methamphetamine in the sewer may at some time in the future be used as a forensic tool, giving law enforcement officials probable cause to obtain a search warrant or to declare a property a public nuisance. The data potentially resulting from deployment of POCIS devices within the sewage system are intended to be an additional tool in the arsenal of law enforcement officials to address the devastating social problem of methamphetamine abuse. The data could potentially affect search and seizure laws, allowing property searches if drugs are detected. Law enforcement officers could petition a judge for a search warrant based on POCIS findings, but as with all cases, the search warrant can be denied. The legal system (judges, lawyers, and jurors) will ultimately judge the admissibility and application of POCIS data in a case. This report is an initial step; much additional research into method validation would be required before this approach is verified for forensic applications. 4. Conclusions This research provides the first report that it is feasible to use passive sampling devices in the sewage collection system to identify the presence or absence of an analyte-of-interest—in this case methamphetamine. Qualitative (presence/absence), as opposed to quantitative, detection of methamphetamine in a sewer line using POCIS passive sampling technology was demonstrated. The probability of finding methamphetamine within the sewer system was maximized by locating the samplers near known sites of illicit activities, although it was not possible using this approach to distinguish between manufacturing or recreational abuse of methamphetamine. However, both are illegal in the US. This research could potentially affect search and seizure laws, allowing property searches if drugs are detected, and stimulates discussion of the ethical and legal aspects of this scientific approach. In future research, precursor chemicals used for the production of methamphetamine could be sampled by POCIS devices in sewer lines. Passive sampling devices should be placed in sewer lines at sites where ATSs or other illicit drug use or manufacture is suspected as well as upstream of suspected sites. This technique could be expanded to monitor the sewage distribution system for other chemicals-of-interest (legal pharmaceuticals and personal care products, legal and illegal industrial chemical discharges, etc.). Calibration and validation of passive sampling devices would be required, even under such harsh conditions as would be encountered in sewers. In addition, hot spot areas contributing significant amounts of drugs or industrial chemicals could be identified and water pretreatment processes could be initiated before the sewage reaches the wastewater treatment plant. Acknowledgments The authors would like to acknowledge the funding from the U.S. Department of Justice — COPS program for the purchase of the triple quadrupole HPLC–MS/MS instrumentation that made this research possible. We wish to acknowledge the laboratory assistance of Gene Mullins and the graphical assistance of Amy Knox. We would like to
thank the personnel at the Cookeville Wastewater Treatment Plant, Cookeville, TN, USA, for their willingness to aid this research in passive sampler placement and retrieval; and, acknowledge the assistance of Tammy L. Jones-Lepp for her review and discussion of this manuscript. References 109th Congress Report, House of Representatives. The library of congress. Available at http://www.gpo.gov/fdsys/pkg/CRPT-109hrpt42/html/CRPT-109hrpt42.htm. [Verified June 2013]. Alvarez DA, Petty JD, Huckins JN, Jones-Lepp TL, Getting DT, Goddard JP, et al. Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments. Environ Toxicol Chem 2004;23:1640–8. Alvarez DA, Stackelberg PE, Petty JD, Huckins JN, Furlong ET, Zaugg SD, et al. Comparison of a novel passive sampler to standard water-column sampling for organic contaminants associated with wastewater effluents entering a New Jersey stream. Chemosphere 2005;61:610–22. Alvarez DA, Huckins JN, Petty JD, Jones-Lepp T, Stuer-Laridsen F, Getting DT, et al. Tool for monitoring hydrophilic contaminants in water: polar organic chemical integrative sampler (POCIS). In: Greenwood R, Mills G, Vrana B, editors. Comprehensive analytical chemistry, vol. 48. Amsterdam: Elsevier; 2007. p. 171–97. Alvarez DA, Rosen MR, Perkins SD, Cranor WL, Schroeder VL, Jones-Lepp TL. Bottom sediment as a source of organic contaminants in Lake Mead, Nevada, USA. Chemosphere 2012;88(5):605–11. Bartelt-Hunt SL, Snow DD, Damon T, Shockley J, Hoagland K. The occurrence of illicit and therapeutic pharmaceuticals in wastewater effluent and surface waters in Nebraska. Environ Pollut 2009;157(3):786–91. Bartelt-Hunt SL, Snow DD, Damon-Powell T, Brown DL, Prasai G, Schwarz M, et al. Quantitative evaluation of laboratory uptake rates for pesticides, pharmaceuticals, and steroid hormones using POCIS. Environ Toxicol Chem 2011;30(6):1412–20. Boles TH, Wells MJM. Analysis of amphetamine and methamphetamine as emerging pollutants in wastewater and wastewater-impacted streams. J Chromatogr A 2010;1217: 2561–8. Castiglioni S, Zuccato E. Illicit drugs as emerging contaminants. In: Halden RU, editor. Contaminants of emerging concern in the environment: ecological and human health considerations. American chemical society symposium seriesWashington, DC: American Chemical Society; 2010. p. 119–36. Castiglioni S, Zuccato E, Chiabrando C, Fanelli R, Bagnati R. Mass spectrometric analysis of illicit drugs in wastewater and surface water. Mass Spectrom Rev 2008;27(4): 378–94. “Cleanup of methamphetamine contaminated properties,” Tennessee Department of Environment & Conservation, Department of Remediation. Available at http://www.tn. gov/environment/dor/meth/ [Verified June 2013] “Drug fact sheet: methamphetamine”, U.S. Drug Enforcement Administration, U.S. Department of Justice. Available at http://www.justice.gov/dea/druginfo/ drug_data_sheets/Methamphetamine.pdf [Verified June 2013]. Harman C, Reid M, Thomas KV. In situ calibration of a passive sampling device for selected illicit drugs and their metabolites in wastewater, and subsequent year-long assessment of community drug usage. Environ Sci Technol 2011;45(13):5676–82. Harman C, Allan IJ, Vermeirssen ELM. Calibration and use of the polar organic chemical integrative sampler—a critical review. Environ Toxicol Chem 2012;31(12):2724–38. Jones-Lepp TL, Alvarez DA, Petty JD, Huckins JN. Polar organic chemical integrative sampling and liquid chromatography-electrospray/ion-trap mass spectrometry for assessing selected prescription and illicit drugs in treated sewage effluents. Arch Environ Contam Toxicol 2004;47:427–39. Jones-Lepp TL, Sanchez C, Alvarez DA, Wilson DC, Taniguchi-Fu R-L. Point sources of emerging contaminants along the Colorado River Basin: source water for the arid Southwestern United States. Sci Total Environ 2012;430:237–45. Kasprzyk-Hordern B. Occurrence of illicit drugs in surface water and wastewater in the UK. In: Castiglioni S, Zuccato E, Fanelli R, editors. Illicit drugs in the environment: occurrence, analysis, and fate using mass spectrometry (Wiley series on mass spectrometry). Hoboken, NJ: John Wiley and Sons, Inc.; 2011. p. 153–70. Mills GA, Vrana B, Allan I, Alvarez DA, Huckins JN, Greenwood R. Trends in monitoring pharmaceuticals and personal-care products in the aquatic environment by use of passive sampling devices. Anal Bioanal Chem 2007;387:1153–7. Petty JD, Huckins JN, Alvarez, DA. Device for sequestration and concentration of polar organic chemicals from water. U.S. Patent 6,478,961, filed June 15, 2001, and issued November 12, 2002. United States Environmental Protection Agency (USEPA). RCRA hazardous waste identification of methamphetamine production process by-products. Report to congress under the USA PATRIOT Improvement and Reauthorization Act of 2005. Washington D.C.: OERR; 2008 van Nuijs ALN, Castiglioni S, Tarcomnicu I, Postigo C, de Alda ML, Neels H, et al. Illicit drug consumption estimations derived from wastewater analysis: a critical review. Sci Total Environ 2011;409(19):3564–77. Vazquez-Roig P, Blasco C, Picó Y. Advances in the analysis of legal and illegal drugs in the aquatic environment. TrAC Trends Anal Chem 2013;50:65–77. Zuccato E, Castiglioni S. Illicit drugs in the environment. Philos Trans R Soc A Math Phys Eng Sci 2009;367(1904):3965–78. Zuccato E, Castiglioni S. Assessing illicit drug consumption by wastewater analysis: history, potential, and limitation of a novel approach. In: Castiglioni S, Zuccato E, Fanelli R, editors. Illicit drugs in the environment: occurrence, analysis, and fate using mass spectrometry (Wiley series on mass spectrometry). Hoboken, NJ: John Wiley and Sons, Inc.; 2011. p. 291–304.
Contents lists available at ScienceDirect
Science of the Total Environment journal homepage: www.elsevier.com/locate/scitotenv
Short Communication
Pilot survey of methamphetamine in sewers using a Polar Organic Chemical Integrative Sampler Tammy H. Boles a,1, Martha J.M. Wells a,b,⁎,2 a b
Department of Chemistry, Tennessee Technological University, Cookeville, TN 38505, USA Center for the Management, Utilization and Protection of Water Resources, Tennessee Technological University, Cookeville, TN 38505, USA
H I G H L I G H T S
G R A P H I C A L
A B S T R A C T
• Polar Organic Chemical Integrative Samplers (POCIS) were deployed into sewer lines. • Proof-of-concept was established for using POCIS devices in the sewage system. • POCIS sorbent extracts were analyzed via HPLC–MS/MS. • Methamphetamine was detected within the sewage collection system. • The data encourage research for future use as a forensic tool in law enforcement.
a r t i c l e
i n f o
Article history: Received 4 July 2013 Received in revised form 31 October 2013 Accepted 31 October 2013 Available online xxxx Keywords: Methamphetamine Passive sampler Sewer Forensic Wastewater
a b s t r a c t A pilot study for the qualitative detection of methamphetamine at sites within a sewage collection system adjacent to locations suspected to harbor illegal drug activities was investigated and preliminary findings are reported. Sewage samples were collected over a time interval of four weeks using a Polar Organic Chemical Integrative Sampler (POCIS) deployed directly into the sewer line. The POCIS sorbent was extracted and analyzed via high-performance liquid chromatography tandem mass spectrometry (HPLC–MS/MS). Methamphetamine was found in sewage from one of three sampling sites at a concentration greater than the HPLC–MS/MS method detection limit (MDL) of 3 ng/mL. The goal of this research was to establish proof-of-concept of the feasibility for sampling and analysis using POCIS devices in the sewage collection system. The data encourage further testing and research. The ability to pinpoint the presence of methamphetamine in the sewer may in the future be used as a forensic tool in law enforcement. © 2013 Elsevier B.V. All rights reserved.
1. Introduction
⁎ Corresponding author. E-mail addresses: [email protected] (T.H. Boles), [email protected], [email protected] (M.J.M. Wells). 1 Present address: School of Environmental Studies, Tennessee Technological University, Cookeville, TN 38505, USA. 2 Present address: EnviroChem Services, 224 Windsor Drive, Cookeville, TN 38506, USA. 0048-9697/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.scitotenv.2013.10.122
Methamphetamine — also known as “meth,” “speed,” and “crank,” — is a highly addictive, powerful nervous system stimulant. Because methamphetamine is so addictive, it is illegal to manufacture or use methamphetamine, except by prescription, under U.S. Federal Law. In the United States, the Drug Enforcement Administration (DEA) classified methamphetamine as a Schedule II substance, available only by prescription but
10
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rarely prescribed (DEA Fact Sheet: Methamphetamine, 2013). Methamphetamine is illegally sold in pill, capsule, powder, and chunk form. In its pure form, the hydrochloride salt of methamphetamine is yellow to colorless, although the street drug may be colored due to impurities. The drug can be created cheaply and easily in clandestine, “clan,” labs and can be smoked, snorted, inhaled, or injected. Because methamphetamine is so cheap and easy to produce, clandestine labs have proliferated and have been found in all states of the United States. In 1993, DEA officials estimated that 218 labs existed; in 2004 almost 15,000 labs were seized (109th Congress Report, House of Representatives, 2013). In Tennessee, USA, law enforcement agencies across the state have encountered approximately 7600 clandestine methamphetamine labs from 1998 to present (Cleanup of Methamphetamine Contaminated Properties, 2013). Illicit drugs, such as methamphetamine, can enter source waters through wastewater treatment plant effluents (i.e., human excretion), and via manufacturing in clandestine laboratories (USEPA, 2008). Pharmaceutical and personal care products (PPCPs) in the environment are not regulated in the United States but enter the urban water cycle and have the potential to negatively affect water quality. Upon contamination of a water source, methamphetamine produced in a clandestine laboratory cannot be distinguished from methamphetamine consumed and excreted by humans. Based on published reviews from both the United States and Europe (Vazquez-Roig et al., 2013; Zuccato and Castiglioni, 2009, 2011; Kasprzyk-Hordern, 2011; van Nuijs et al., 2011; Castiglioni and Zuccato, 2010; Boles and Wells, 2010; Castiglioni et al., 2008), measurable concentrations of amphetamine and methamphetamine — two of a class of drugs known as amphetamine-type stimulants (ATSs) — have been found in wastewater, biosolids, surface water, and sediment. Local news reports have chronicled several instances of clandestine methamphetamine laboratories and arrests for methamphetamine possession and abuse, lending credence to the hypothesis that it would be found in wastewater. However, no previous studies have been conducted to detect the presence of methamphetamine directly from sewer pipes. Wastewater and surface water samples for research are generally collected through traditional water sampling techniques, such as grab sampling or composite water sampling. A grab sample is collected simultaneously in its entirety and reflects a single data point in time, while a composite sample involves collecting discrete samples taken at specific intervals of time and combining them at the end of the sampling period into a single sample. The composite sample reflects an average concentration of the analyte in the water source over the sampling time period. However, grab samples, and even composite samples, only capture information at that moment or over a specified short sampling period. In addition, grab and composite sampling techniques may miss important events, such as high or low flow, precipitation, and variability in chemical loading. As an alternative, passive sampling devices are being used to monitor hydrophilic/hydrophobic contaminants such as pesticides, PPCPs, and illicit drugs in aqueous environments, and are designed to stay in the aqueous environment for several days, weeks, or even months (Harman et al., 2012). The Polar Organic Chemical Integrative Sampler (POCIS) device combines the ability to integrate exposure over time during a range of hydrologic conditions with the ability to accumulate a detectable mass of a compound that may be present in a water sample at concentrations below the method detection level (Alvarez et al., 2005). The design of the POCIS device allows it to mimic the exposure of the respiratory system of aquatic organisms to dissolved chemicals (Alvarez et al., 2004). POCIS samplers have been employed for quantitative identification of numerous wastewater-related contaminants, including methamphetamine in surface water (Jones-Lepp et al., 2012; Bartelt-Hunt et al., 2009), sediment (Alvarez et al., 2012), and wastewater (Harman et al., 2011; Bartelt-Hunt et al., 2009; Jones-Lepp et al., 2004). POCIS sampling rates (a value needed for quantitative backcalculation of environmental concentrations) have been determined
for some compounds, including methamphetamine (Bartelt-Hunt et al., 2009, 2011; Harman et al., 2011; Alvarez et al., 2007). However, even though the membrane in POCIS devices is not as subject to biofouling as other membrane types (Alvarez et al., 2004), biofouling can still occur, causing uptake kinetics and subsequently, laboratory-derived calibration data to be modified (Mills et al., 2007). The goal of this research was to establish a proof-of-concept regarding the feasibility for sampling and analysis in the sewage collection system and to provide a qualitative assessment of the occurrence of methamphetamine using POCIS, because raw sewage near the source is not as dilute as wastewater influent, and is more likely to cause biofouling of the POCIS device. Therefore, the research reported in this paper focuses on the preliminary findings from a pilot study that used POCIS devices to monitor raw sewage for methamphetamine in the sewage collection system before the raw sewage reaches a wastewater treatment plant. The ability to pinpoint the location of methamphetamine in the sewer may at some time in the future be used as a forensic tool in law enforcement. 2. Material and methods 2.1. POCIS deployment and sampling Sampling occurred at sites in Cookeville, TN, USA that were known hotspots for drug activity because information about methamphetamine-related arrests is published regularly in the local newspaper. POCIS devices were deployed in three different sewer lines originating from three buildings suspected to harbor illegal drug activities. For privacy purposes, the sites will be referred to as Site 1, Site 2, and Site 3. Although deployment canisters can be used to house the devices, the small size of the sewer pipes tested in this research prevented the use of canisters, such that two devices were held together with a plastic zip tie and were placed inside city-owned sewer lines at the junction between the private sewer line and the city-owned line. The samplers were deployed for a total sampling period of 27 days. 2.2. POCIS characteristics AQUASENSE-P POCIS devices were obtained from Environmental Sampling Technologies (St. Joseph, MO) as based on a patented design (Petty et al., 2002) consisting of 200 mg of Oasis hydrophilic-lipophilic balanced (HLB) sorbent contained between two membranes made of hydrophilic polyethersulfone (PES) with a 0.1 μm pore size and a 41 cm2 surface area. Upper and lower stainless steel support rings are used to seal the device and prevent loss of sorbent. Although two POCIS devices were used for sampling each site, the devices were extracted separately. Extraction of the POCIS devices and HPLC–MS/MS analysis for methamphetamine are described in supplementary data associated with this manuscript. 3. Results and discussion 3.1. Pilot monitoring using POCIS devices The POCIS device configuration used in this research consisted of 200 mg of Oasis HLB sorbent sandwiched between PES membranes with a surface area of 41 cm2 as purchased from the manufacturer. This construction meets standardized surface area to sorbent/lipid volume (SA/V) specifications described by Alvarez et al. (2007, 2012). Pharmaceutical POCIS devices are designed to be appropriate for most pharmaceuticals and contain only HLB sorbent, as opposed to the pesticide POCIS devices that contain three different sorbents and target pesticides as well as hormones and wastewater treatment chemicals. HLB sorbents are made by polymerizing divinylbenzene (lipophilic) and N-vinylpyrrolidine (hydrophilic) monomers. They are capable of extracting acidic, basic and neutral analytes, which may be polar or
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nonpolar. Methamphetamine — a weak base — is a 2° amine with a pKa = 10.38. No sorbents other than HLB were tested in this research. In late summer, two POCIS devices each were deployed in sewer lines originating from three buildings suspected to harbor illegal drug activities referred to as Site 1, Site 2, and Site 3. The devices were placed inside city-owned sewer lines at the junction between the private sewer line and the city-owned line. The samplers were retrieved after a total sampling time of 27 days (Petty et al., 2002). POCIS devices from Site 1 (Fig. 1) and Site 2 were extremely dirty with a visible accumulation of slime on the PES membrane. One of the POCIS devices from Site 1 had a puncture through one side of the membrane. POCIS devices from Site 3 were only slightly soiled. Analysis of the sample from Site 1 was positive for the presence of methamphetamine (see Supplementary data). The data support the conclusion that methamphetamine was present in the sewer line from Site 1 and that, qualitatively, it was present at concentrations greater than the method detection limit (MDL) of 3 ng/mL. The sample extract from Site 2 was not positive for methamphetamine. Site 3 POCIS devices were only slightly dirty; the sorbent was not discolored and did not appear to have been wetted. The appearance of the device and sorbent suggest minimal, if any, sewage flow across the device. At Site 3, the POCIS device may have been improperly positioned or no sewage flowed across the POCIS device during the time it was deployed. 3.2. Qualitative versus quantitative measurement of target analyte concentration In other studies, POCIS devices have been employed for quantitative identification of environmental concentrations of methamphetamine in surface water (Jones-Lepp et al., 2012; Bartelt-Hunt et al., 2009), sediment (Alvarez et al., 2012), and wastewater (Harman et al., 2011; Bartelt-Hunt et al., 2009; Jones-Lepp et al., 2004). However, in this research, due to the nature of the sewer line sites sampled, qualitative
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assessment only of the presence or absence of methamphetamine above a threshold level was appropriate for POCIS deployment in the sewer system and adequate to meet the goals of this project. In situ quantitative application of POCIS data for the assessment of environmental concentrations is based on certain assumptions: the POCIS device is submerged during the entire deployment period, the average flow rate during the length of deployment is known, the turbulence or lack thereof for the site is known, sorption of the analyte is based upon linear uptake rate kinetics, fluctuations in temperature are small, and biofouling is minimal. For complete quantitative calculation of analyte concentration after environmental exposure of a POCIS device, the content of the POCIS sorbent is analyzed and that data is used to back-calculate a time-weighted average concentration at the site deployed based on (1) the uptake rate of the specific analyte and (2) the flow rate of the environmental compartment (Alvarez et al., 2007). The uptake or sampling rate for methamphetamine on standard POCIS devices has been determined and reported (Bartelt-Hunt et al., 2009, 2011; Harman et al., 2011; Alvarez et al., 2007) based on calculation (Bartelt-Hunt et al., 2009), laboratory calibration (Bartelt-Hunt et al., 2011; Alvarez et al., 2007), or field-deployed environmental conditions (Harman et al., 2011). However, the sampling rate for methamphetamine is not established for a sewer line. The stability of methamphetamine during the sampling time is not known—the extent to which methamphetamine is degraded after sorption is uncertain. However, if methamphetamine were present on the sorbent but degraded below the detection limit during deployment, a false negative result would be reported. Additionally, the average flow rate of the environmental compartment is indeterminate for sampling in a sewer line compared to surface water or wastewater field sites. The average flow rate in the sewer lines sampled in this research could have varied substantially during the deployment of the device. The device may not have been submerged during the entire deployment period, and it may be envisioned that conditions during deployment varied between quiescent and turbulent flows in the sewer line. For these reasons, qualitative assessment of the presence or absence of the target analytes is presented here rather than complete quantitative determination. Because the fundamental assumptions regarding deployment were not established and the potential degradation of the analyte is unknown, back-calculation to determine the concentration during deployment was not conducted and qualitative assessment only of the sampling results is reported. In the future, issues of flow rate, submersion, and turbulence in the sewer lines may be determined to render it possible to quantitatively calculate time-weighted average concentrations. Meanwhile, qualitative application, as in this research, is shown to be feasible. Analytically, it is not possible to distinguish the methamphetamine originating from human excrement from that produced in an illegal laboratory. Characteristic synthetic precursors and by-products of methamphetamine manufacturing could additionally be monitored in the future to verify the presence of a clandestine laboratory. However, the proof-ofconcept of the deployment of POCIS devices as qualitative samplers indicating the presence/absence of an analyte-of-interest in sewer lines was demonstrated. 3.3. Ethical and legal aspects of this study
Fig. 1. POCIS devices after deployment in sewer lines for one month and initial external cleaning.
As in this report, scientific advancement often outpaces associated ethical and legal questions. Herein, a new scientific approach to monitoring the presence/absence of an illegal chemical substance within the sewage distribution system prior to reaching its destination in a municipal sewage treatment plant is reported. The methodologies employed here were determined to be scientifically feasible, but questions can be raised as to the ensuing ethical and legal aspects of this study. In summary, sampling occurred in municipal areas near commercial buildings that were known hotspots for illegal drug activity because information about arrests is published in the local newspaper. No individual
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households were targeted in this research. For privacy purposes, no maps or other identifying information was provided in this manuscript—sites were referred to as Site 1, Site 2, and Site 3. Devices were placed inside city-owned sewer lines at the junction between private and city-owned sewer lines. At no time were private property sewer lines breached. Permission to deploy the POCIS devices was granted by the municipal sewerage company. Wastewater treatment plant sampling (influent and effluent) is reported with frequency in the literature. However, this research raises ethical questions regarding privacy and targeting sources when sampling upstream of the wastewater treatment plant, and should promote discussion of these matters. The data collected in this pilot study was intended only to establish the scientific feasibility of this application, and was not used in a legal case. The ability to pinpoint the location of methamphetamine in the sewer may at some time in the future be used as a forensic tool, giving law enforcement officials probable cause to obtain a search warrant or to declare a property a public nuisance. The data potentially resulting from deployment of POCIS devices within the sewage system are intended to be an additional tool in the arsenal of law enforcement officials to address the devastating social problem of methamphetamine abuse. The data could potentially affect search and seizure laws, allowing property searches if drugs are detected. Law enforcement officers could petition a judge for a search warrant based on POCIS findings, but as with all cases, the search warrant can be denied. The legal system (judges, lawyers, and jurors) will ultimately judge the admissibility and application of POCIS data in a case. This report is an initial step; much additional research into method validation would be required before this approach is verified for forensic applications. 4. Conclusions This research provides the first report that it is feasible to use passive sampling devices in the sewage collection system to identify the presence or absence of an analyte-of-interest—in this case methamphetamine. Qualitative (presence/absence), as opposed to quantitative, detection of methamphetamine in a sewer line using POCIS passive sampling technology was demonstrated. The probability of finding methamphetamine within the sewer system was maximized by locating the samplers near known sites of illicit activities, although it was not possible using this approach to distinguish between manufacturing or recreational abuse of methamphetamine. However, both are illegal in the US. This research could potentially affect search and seizure laws, allowing property searches if drugs are detected, and stimulates discussion of the ethical and legal aspects of this scientific approach. In future research, precursor chemicals used for the production of methamphetamine could be sampled by POCIS devices in sewer lines. Passive sampling devices should be placed in sewer lines at sites where ATSs or other illicit drug use or manufacture is suspected as well as upstream of suspected sites. This technique could be expanded to monitor the sewage distribution system for other chemicals-of-interest (legal pharmaceuticals and personal care products, legal and illegal industrial chemical discharges, etc.). Calibration and validation of passive sampling devices would be required, even under such harsh conditions as would be encountered in sewers. In addition, hot spot areas contributing significant amounts of drugs or industrial chemicals could be identified and water pretreatment processes could be initiated before the sewage reaches the wastewater treatment plant. Acknowledgments The authors would like to acknowledge the funding from the U.S. Department of Justice — COPS program for the purchase of the triple quadrupole HPLC–MS/MS instrumentation that made this research possible. We wish to acknowledge the laboratory assistance of Gene Mullins and the graphical assistance of Amy Knox. We would like to
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