J. A.
Soller
*a,
M. H.
Nellor
b,
C. J.
Cruz
c and
E.
McDonald
d
aSoller Environmental, 3022 King St, Berkeley, CA, USA. E-mail: jsoller@sollerenvironmental.com
bNellor Environmental Associates, Inc., 4024 Walnut Clay Dr, Austin, TX, USA
cSeparation Processes, Inc., 3156 Lionshead Avenue, Suite 2, Carlsbad, CA, USA
dAlan Plummer Associates, Inc., 1320 South University Dr, Suite 300, Fort Worth, TX, USA
First published on 3rd June 2015
Quantitative relative risk assessment (QRRA) evaluations were conducted for two hypothetical direct potable reuse (DPR) case studies. The goal of a risk assessment is to estimate the severity and likelihood of harm to human health or the environment occurring from exposure to a risk agent. Each case study compares a No Project Alternative (raw water that has undergone drinking water treatment) with a potential DPR Alternative (treated wastewater that has undergone advanced water treatment and drinking water treatment). Neither DPR scenario accounts for blending with raw drinking water prior to drinking water treatment, blending after drinking water treatment in the potable distribution system, or blending via directly distributing the purified reclaimed water into a drinking water distribution system. The QRRA focuses on chemicals that are currently regulated and chemicals that are not yet regulated but are of broad interest, such as pharmaceuticals and personal care products. Pathogen risk evaluation was not conducted but could follow a similar approach. The results illustrate how QRRA can inform water supply decisions that are made with respect to industrial pretreatment/source control, wastewater treatment, drinking water treatment, and advanced treatment for DPR. In these case studies, the DPR alternatives are projected to provide protection from regulated constituents and constituents of emerging concern that are comparable to or better than the No Project Alternatives. The results also indicate that future QRRA studies would benefit from specific information that could be obtained through targeted research.
Water impactTo assist in understanding and communicating the potential associated with direct potable reuse (DPR), one important tool is the quantitative relative risk assessment (QRRA) approach. Exposure to chemical constituents is very difficult to precisely estimate. A QRRA eliminates this issue by using a hypothetical, standardized exposure and provides a more health protective approach than traditional risk assessments because it uses observed concentrations for developing exposure that are greater than those that would actually occur. This paper provides examples of how QRRAs can evaluate the relative risks of two different DPR schemes for regulated constituents and constituents of emerging concern. The results can inform decisions regarding industrial pretreatment/source control and wastewater treatment, drinking water treatment, and advanced treatment schemes for DPR. |
Initial reclaimed water uses were primarily for irrigation of agriculture. Today, reclaimed water is used for a wide range of beneficial purposes including power plant cooling water, commercial and municipal irrigation, river and stream flow enhancement, natural gas exploration activities, and augmentation of drinking water supplies (potable reuse). For example, water reuse will provide approximately 1.53 million acre-feet per year of water supply in the State of Texas (USA) by the year 2060 and will meet approximately 18% of the projected water needs for the State.1 There is significant potential for additional development of water reuse as a water management strategy. Much of this potential may be realized through the development of potable reuse projects, particularly as progress is made in communicating the advantages, benefits and safety of potable reuse to the public.
Indirect potable reuse (IPR) is the use of reclaimed water for potable purposes by discharging to a water supply source, such as a surface water or groundwater. The mixed reclaimed and natural waters then receive additional treatment before entering the drinking water distribution system. On the other hand, direct potable reuse (DPR) is the introduction of reclaimed water either directly into the potable water distribution system or into the raw water supply entering a drinking water treatment plant. Whereas numerous IPR projects have been successfully implemented, DPR implementation is much less common. However, for various reasons including severe droughts, increased population, and increased confidence in water treatment technologies, many municipalities are now considering DPR.
Herein, we conduct demonstration quantitative relative risk assessment (QRRA) evaluations for two hypothetical DPR projects (case studies) to illustrate how these types of assessments can be conducted and how the information can be applied to provide a human health context to monitoring data for chemicals that are currently regulated or are unregulated.
The DPR Project Alternative is defined as secondary/tertiary wastewater treatment plant (WWTP) effluent which is the feed water to an AWTF that consists of microfiltration (MF) or ultrafiltration (UF), ozone, BAC, and chlorination (Fig. 1). This product water is then treated by the enhanced WTP (described above) consisting of ozone, BAC, flocculation-sedimentation, media filtration, and chlorination.
The DPR Project Alternative is defined as secondary/tertiary WWTP effluent which is the feed water to an AWTF that consists of MF or UF, RO, and advanced oxidation (ultraviolet (UV) irradiation and hydrogen peroxide) (Fig. 2). This product water is then treated by a WTP consisting of flocculation-sedimentation, media filtration, and chlorination.
To simulate the case studies for the QRRA, it was first necessary to collect water quality data. Monthly samples were collected from two raw drinking waters in the State of Texas and secondary/tertiary effluent from two WWTPs for the period December 2013 through May 2014. Samples were analyzed for regulated constituents (Clean Water Act priority pollutants, constituents with federal drinking water maximum contaminant levels (MCLs), and constituents with other regulatory recommendations or guidelines), and unregulated constituents (for example, prescription drugs, over-the-counter drugs, and ingredients in personal care products). For the QRRA, “detected compounds” are those that were found in at least one sample at or above the compound-specific Minimum Reporting Level (MRL). The MRL represents an estimate of the lowest concentration of a compound that can be quantitatively measured. For each constituent, if the concentration in at least one sample was at or above the MRL it was deemed to be “detected.” If the other sample concentrations were reported to be below the MRL, for calculation of the average concentration for the QRRA, the constituent was assumed to be present at the MRL. This simple approach is likely to overestimate the concentration of any observation reported below the MRL compared to a more rigorous statistical treatment.8 However, this straightforward approach is parsimonious, builds off of prior successful QRRA applications, and provides a reasonable and defensible basis from which risk managers can make practical decisions.3–7
For the QRRA, four fundamental steps were carried out during the course of this assessment. Those steps follow the general guidance provided by the U.S. Environmental Protection Agency (U.S. EPA) for chemical risk assessment9,10 and are as follows: (1) evaluate data and identify detected chemicals that can be used to represent the potential carcinogenic and noncarcinogenic hazard posed by the test waters; (2) conduct a toxicity assessment of the potential carcinogenicity and noncarcinogenic effects of the chemicals of concern; (3) conduct an exposure assessment, which for this study involves calculating potential doses based on estimated concentrations and an assumed standard intake of water; and 4) characterize the potential health risks associated with the test waters.
For the data evaluation, detected constituents were divided into two categories. Constituents of Potential Concern (CPCs) are detected compounds that are regulated or currently under consideration for regulation and had associated health-based criteria that could be used to quantify the estimated relative potential health risk. Constituents of Emerging Concern (CECs) are detected compounds that are unregulated with published toxicity information to evaluate their health significance. The Eurofins Eaton Analytical method was used for analysis because it is capable of reliably testing for more than 90 CECs in a single method at low levels (ng L−1).
For the No Project alternatives, estimated WTP unit process removal efficiencies were applied to the CPCs and CECs in the raw waters to estimate resultant drinking water concentrations. For the DPR alternatives, estimated AWTF unit process and WTP unit process removal efficiencies were applied to the CPCs and CECs in the secondary wastewaters to estimate resultant drinking water concentrations.11 This assessment did not account for formation of DBPs, such as trihalomethanes or N-nitrosodimethylamine through the various water treatment processes.
The purpose of the toxicity assessment is to weigh available evidence regarding the potential for a particular chemical to cause adverse health effects in exposed individuals and to provide, where possible, an estimate of the relationship between the extent of exposure to a chemical and the increased likelihood and/or severity of adverse health effects.4 Detected chemical constituents were evaluated for their carcinogenic and noncarcinogenic potential based on a hazard identification and a dose–response evaluation. From this evaluation, toxicity values for CPCs (characterized in terms of reference doses [RfDs] for noncarcinogenic effects and carcinogenic oral slope factors [SFs] for carcinogenic effects) were identified to estimate the potential for adverse effects as a function of human exposure to a given constituent. In addition, risk based action levels (RBALs) were collated from the literature for CECs. The health-based criteria were used as input to the QRRA to quantify the estimates of relative potential risk from the No Project and DPR alternatives.
The objective of an exposure assessment is to estimate the type and magnitude of exposure to the constituents of concern. For this relative risk assessment study, which strictly focused on exposure through drinking water, a hypothetical exposure was calculated based on observed average concentrations of the CPCs and CECs in raw water or wastewater and their predicted concentrations in drinking water taking into consideration removal efficiencies of treatment processes through water treatment and combined advanced treatment and water treatment, and a standard ingestion volume to compare the various scenarios under investigation. For the purposes of this exposure assessment, the daily volume of water ingested is assumed to be a constant 1.2 L.12,13
Risk assessment methods used in this study compare water sources where the hypothetical exposures used in the assessment are not expected to actually occur, but are used to “normalize” exposure between the existing drinking water and the hypothetical alternative. Although stochastic methods may be used to estimate situational exposure effectively, the hypothetical alternative scenarios present a high degree of uncertainty since there is no method of determining long-term, realistic consumption. There are also many confounding factors that impact exposure and public health that cannot be quantified, such as bottled water usage, smoking, diet, exercise regimen, etc. Other routes of exposure, such as dermal absorption and inhalation may also be valid, but are not the focus of this investigation.
For CPCs, QRRAs were conducted for noncarcinogenic and carcinogenic risk. For noncarcinogenic risk, the QRRA evaluated the cumulative hazard index ([HI] – the sum of hazards for each CPC) for each case study alternative, where a result greater than or equal to 1 is the threshold for potential adverse health effects. Carcinogenic risks are estimated as the incremental probability of an individual developing cancer over a lifetime as a result of exposure to a potential carcinogen based on its cancer SF. Cancer SFs are based on experimental animal data and limited epidemiological studies, when available. The model generally used by the U.S. EPA to calculate numerical cancer potency values over predicts risk in comparison to average population risk.
For CECs, the 2012 National Research Council (NRC) risk exemplar approach was utilized to assess risk (NRC, 2012). The risk exemplar approach relies on estimates of the amount of a substance in drinking water that can be ingested daily over a lifetime without appreciable risk. These “safe” levels are called Drinking Water Equivalent Levels (DWELs), Predicted No Effect Concentrations (PNECs), or Drinking Water Guidelines (DWGs). For each of the detected CECs, potential lifetime health risks were assessed by calculating margins of safety (MOSs).14 A MOS is the ratio of a risk-based action level (RBAL) based on a DWEL, PNEC, DWG or other available heath benchmark, divided by the estimated concentration of the constituent in water. In using the risk exemplar approach, the NRC opined that an MOS lower than 1 for a specific CEC posed a potential concern from that CEC. This interpretation was made in light of the multiple safety factors, such as the application of uncertainty factors, included in the derivation of the RBALs.
Water | Number of analytes | Total number of observations | Number of observations > MRL | Number of constituents with observations > MRL |
---|---|---|---|---|
Case study 1 raw source water | 347 | 1868 | 212 | 55 |
Case study 1 WWTP effluent | 367 | 1898 | 351 | 97 |
Case study 2 raw source water | 308 | 1861 | 55 | 17 |
Case study 2 WWTP effluent | 373 | 1901 | 321 | 90 |
Case study 1 | Case study 2 | |||
---|---|---|---|---|
No project alternative | DPR alternative | No project alternative | DPR alternative | |
Hazard index (HI) | 0.13 | 0.89 | 0.20 | 0.05 |
# CPCs present with RfD | 16 | 27 | 9 | 22 |
Any single constituent with HI > 1 | No | No | No | No |
Major contributors to overall HI | Fluoride (58%) Nitrate (34%) Aluminum (5%) | Nitrate (73%) Fluoride (22%) Monochloroacetic acid (2%) Strontium (2%) | Fluoride (61%) Nitrate (31%) Arsenic (6%) | Fluoride (37%) Nitrite (28%) Manganese (11%) Molybdenum (7%) Cyanide (7%) |
Any constituent > MCLs | No | No | No | No |
The results of the carcinogenic QRRA are shown in Table 3. Similar to the noncarcinogenic risk assessment, concentrations of CPCs were below MCLs and health advisory levels. The carcinogenic risks for the case study 1 No Project Alternative, case study 1 DPR Alternative, and case study 2 No Project Alternative were in approximately the same range. The carcinogenic risk for the case study 2 DPR Alternative (the membrane AWTF), however, is about an order of magnitude lower. For each alternative, arsenic and DBPs are the major contributors to risk. For the case study 2 DPR Alternative, RO and UV/AOP play an important role in reducing risk through removal of these CPCs. These results highlight the need to consider prevention of DBP formation or removal of DBPs as part of a DPR treatment scheme (beginning with the WWTP through AWTF and WTP).
Case study 1 | Case study 2 | |||
---|---|---|---|---|
No project alternative | DPR alternative | No project alternative | DPR alternative | |
NDMA – N-nitrosodimethylamine. BDCM – Bromodichloromethane. CDBM – Chlorodibromomethane. TCA – Trichloroacetic acid. | ||||
Drinking water risk (point estimate) | 1.3 × 10−6 | 3.9 × 10−6 | 7.0 × 10−6 | 7.3 × 10−7 |
# CPCs with SF | 4 | 8 | 4 | 3 |
Major risk contributors | Arsenic (24%) NDMA (74%) | Arsenic (12%) BDCM (20%) CDBM (18%) NDMA (60%) | Arsenic (85%) BDCM (8%) CDBM (13%) | Arsenic (59%) NDMA (22%) TCA (19%) |
Any constituent present at levels > MCLs or advisory levels | No | No | No | No |
CECs | RBAL (ng L−1) | Category | Reference | CECs | RBAL (ng L−1) | Category | Reference |
---|---|---|---|---|---|---|---|
DCPA – Dimethyl tetrachloroterephthalate. DEET – N,N-diethyl-meta-toluamide. FDA – Food and Drug Administration. MRTD – Maximum Recommended Therapeutic Dose. NSAID – Non-steroidal anti-inflamatory drug. OTC – Over the counter. TCEP – Tris(2-chloroethyl) phosphate. TCPP – Tris(2-chloroisopropyl) phosphate. TDCPP – Tris(1,3-dichloro-2-propyl) phosphate. | |||||||
1,7-Dimethylxanthine | 7.0 × 102 | Caffeine metabolite | Environment Protection and Heritage Council et al., 2008 (ref. 15) | Iopromide | 7.5 × 105 | Imaging contrast agent | Environment Protection and Heritage Council et al., 2008 (ref. 15) |
3-Hydroxycarbofuran | 4.2 × 102 | Metabolite of carbofuran, pesticide | U.S. EPA, 2009 (ref. 16) | Ketoprofen | 1.3 × 104 | NSAID | Nellor et al., 2010 (ref. 17) |
4-tert-Octylphenol | 5.0 × 104 | Intermediate for phenolic resins | Environment Protection and Heritage Council et al., 2008 (ref. 15) | Ketorolac | 8.8 × 107 | NSAID | U.S. FDA MRTD Database (ref. 18) |
Acesulfame-K | 5.3 × 108 | Non calorie sweetner | U.S. FDA, 1988 (ref. 19) | Lidocaine | 1.1 × 108 | OTC pain reliever | Donald & Derbyshire, 2004 (ref. 20) |
Acetaminophen | 1.2 × 107 | Analgesic | Intertox, 2009 (ref. 21) | Lincomycin | 3.7 × 105 | Antibiotic | Schwab et al., 2005 (ref. 22) |
Albuterol | 4.1 × 104 | Bronchodilator | Schwab et al., 2005 (ref. 22) | Lopressor | 2.3 × 108 | Beta blocker; blood pressure medication | U.S. FDA MRTD Database (ref. 18) |
Amoxicillin | 1.5 × 103 | Antibiotic | Environment Protection and Heritage Council et al., 2008 (ref. 15) | Meprobamate | 2.6 × 105 | Skeletal muscle relaxant | Snyder et al., 2008 (ref. 23) |
Atenolol | 7.0 × 104 | Beta blocker; blood pressure medication | Snyder et al., 2008 (ref. 23) | Metolachlor | 7.0 × 106 | Herbicide | U.S. EPA, 2009 (ref. 16) |
Azithromycin | 3.9 × 103 | Anitbiotic | Environment Protection and Heritage Council et al., 2008 (ref. 15) | Naproxen | 2.2 × 105 | NSAID | Environment Protection and Heritage Council et al., 2008 (ref. 15) |
Bezafibrate | 3.0 × 105 | Chloesterol medication | Environment Protection and Heritage Council et al., 2008 (ref. 15) | Nifedipine | 1.1 × 109 | Blood pressure and angina medication | U.S. FDA MRTD Database (ref. 18) |
Bisphenol A | 3.5 × 105 | Production of polycarbonate plastics and epoxy resins | U.S. EPA, 2009 (ref. 16) | Pentoxifylline | 1.3 × 105 | Blood circulation medication | Nellor et al., 2010 (ref. 17) |
Butalbital | 1.8 × 108 | Barbiturate | U.S. FDA MRTD Database (ref. 18) | Primidone | 8.4 × 102 | Anti-seizure medication | Intertox, 2009 (ref. 21) |
Caffeine | 8.7 × 107 | Stimulant | Intertox, 2009 (ref. 21) | Quinoline | 1.0 × 101 | Intermediate in the manufacture of other products | U.S. EPA, 2009 (ref. 16) |
Carbamazepine | 1.2 × 104 | Anti-seizure medication | Intertox, 2009 (ref. 21) | Sucralose | 1.7 × 105 | Artificial sweetner | U.S. FDA, 1999 (ref. 24) |
Carisoprodol | 7.0 × 108 | Skeletal muscle relaxant | U.S. FDA MRTD Database (ref. 18) | Sulfadimethoxine | 3.5 × 104 | Anitbiotic | Environment Protection and Heritage Council et al., 2008 (ref. 15) |
Cimetidine | 2.0 × 105 | Heartburn medication, histamine H2-blocker | Environment Protection and Heritage Council et al., 2008 (ref. 15) | Sulfamerazine | 2.3 × 106 | Antibiotic | U.S. FDA MRTD Database (ref. 18) |
Cotinine | 1.0 × 104 | Metabolite of nicotine | Environment Protection and Heritage Council et al., 2008 (ref. 15) | Sulfamethazine | 7.7 × 104 | Antibacterial | Nellor et al., 2010 (ref. 17) |
Diethanolamine | 7.5 × 105 | Ingredient in soaps, cosmetics, shampoos | Schriks et al., 2009 (ref. 25) | Sulfamethoxazole | 1.8 × 107 | Antibiotic | Intertox, 2009 (ref. 21) |
DEET | 8.1 × 104 | Insecticide | Intertox, 2009 (ref. 21) | Sulfathiazole | 7.3 × 105 | Antibacterial | Schwab et al., 2005 (ref. 22) |
Dehydronifedipine | 2.0 × 104 | Metabolite of nifedipine, calcium channel blocker | Environment Protection and Heritage Council et al., 2008 (ref. 15) | TCEP | 4.4 × 103 | Flame retardant | Nellor et al., 2010 (ref. 17) |
Deisopropylatrazine | 1.5 × 102 | Metabolite of atrazine | Nellor et al., 2010 (ref. 17) | TCPP | 1.0 × 104 | Flame retardant | World Health Organization, 2004 (ref. 26) |
Diclofenac | 2.3 × 106 | NSAID | Snyder et al., 2008 (ref. 23) | TDCPP | 2.7 × 103 | Flame retardant | California Department of Toxic Substances Control, 2014 (ref. 27) |
Dilantin | 6.7 × 103 | Anti-seizure medication | Intertox, 2009 (ref. 21) | Theobromine | 2.8 × 1010 | Ingredient in chocolate | U.S. Department of Health and Human Services, 2006 (ref. 28) |
Diltiazem | 6.0 × 104 | Blood pressure medication; calcium channel blocker | Environment Protection and Heritage Council et al., 2008 (ref. 15) | Theophylline | 3.0 × 108 | Bronchodilator | U.S. FDA MRTD Database (ref. 18) |
Erythromycin | 4.9 × 103 | Antibiotic | U.S. EPA, 2009 (ref. 16) | Total DCPA Mono & Diacid Degradate | 3.5 × 105 | Degradation products of herbicide DCPA | U.S. EPA, 2008 (ref. 29) |
Estrone | 4.6 × 102 | Estrogenic hormone | Snyder et al., 2008 (ref. 23) | Triclocarban | 8.8 × 108 | Antibacterial | California Office of Environmental Health Hazard Assessment, 2010 (ref. 30) |
Fluoxetine | 1.0 × 104 | Anti-depressant | Environment Protection and Heritage Council et al., 2008 (ref. 15) | Triclosan | 2.6 × 106 | Antibacterial | Intertox, 2009 (ref. 21) |
Gemfibrozil | 4.6 × 104 | Chloesterol medication | Snyder et al., 2008 (ref. 23) | Trimethoprim | 6.1 × 104 | Antibacterial | Schwab, 2005 (ref. 22) |
Ibuprofen | 3.4 × 104 | NSAID | Nellor et al., 2010 (ref. 17) | Warfarin | 2.3 × 103 | Blood thinner | Schwab, 2005 (ref. 22) |
Iohexal | 7.2 × 105 | Imaging contrast agent | Environment Protection and Heritage Council et al., 2008 (ref. 15) |
Case study 1 | Case study 2 | |||
---|---|---|---|---|
No. project alt. | DPR | No. project alt. | DPR | |
# CECs present > MRL | 32 | 46 | 5 | 53 |
MOS range | 1.6–10500000000 | 0.9–59000000000 | 3600–16000000 | 13–6000000000 |
# CECs with MOS 1–10 | 1 | 1 | 0 | 0 |
CECs with MOS 1–10 | Quinoline | Quinoline | — | 0 |
The RBAL for quinoline, a probable human carcinogen, is based on U.S. EPA's PNEC of 10 ng L−1. Quinoline has specific industrial sources (it is used in the production of dyes, paints, pharmaceuticals, and fragrances), but also has ubiquitous sources including automobile exhaust. Quinoline is biodegradable, removed by RO, and can be photolysized. Thus, if the case study 1 DPR Alternative utilized UV photolysis or RO, it is likely that the concentration would have been further reduced and the MOS would be greater than 1.
For CEC assessments it is important to acknowledge that over time new and updated RBALs are likely to be developed that would further inform risk evaluations, as well as additional information on advanced treatment process performance from research, piloting, or full-scale operations.
This study was not intended to be exhaustive, nor was the intent to try to eliminate all uncertainty regarding the level of risk attributable to drinking water. There are potential pollutants for which data were not available, however the CECs evaluated in this investigation included many of the constituents that have been observed in water supplies or wastewater, and were evaluated based on a reliable analytical method. As new methods mature and other CECs emerge as potential constituents of concern, the methods employed herein can be extended to include additional constituents.
The QRRA results clearly illustrate that for the specific constituents in the risk assessment, RO and UV/AOP can be important treatment processes for the removal and control of DBPs including NDMA.
There are numerous locations worldwide that are considering DPR as an alternative/supplemental source for their water supplies. Each of these communities has specific financial and logistical constraints that are aspects of their risk management considerations. In some cases, communities may be considering DPR options in which the product water from the AWTF is being considered as a direct component of the drinking water supply rather than as a source water to be subsequently treated at a drinking water facility prior to distribution. This study does not address the relative risks of implementing DPR in this way. However, the approach described and illustrated here could serve as a template for evaluating the relative risks of implementing DPR in ways not specifically evaluated herein.
This journal is © The Royal Society of Chemistry 2015 |