United States Environmental Protection \r ^1 Agency Office of Water www.epa.gov April 2021 Report on the Elemental Analyses of Samples from the Targeted National Sewage Sludge Survey 1 H Hydrogen J .0079 3 Li 4 Be lithium 6A41 94)1 s" 11 Na Sodium 223897 12 Mg Magnesium 24.305 19 K ¦ 20 Ca Calcium 40.078 ®Rb 38 Sr Rubidium 85.4678 Strontium 87.62 55 Cs 56 Ba Cesium 132.9055 Barium J 37327 87 Fr 88 Ra Francium (223) Radhjm (226) H Si C P i O v 22 Ti Titanium 47.867 23 V Vanadium 50.9415 24 Cr Chromium 51.9961 25 Mn Manganese 54.938 26 Fe iron 55345 27 Co CobaMfl 28 Nil-'J 1 is* 30 Zn Zinc 40 Zr Zirconium 91.224 41 Nb Niobium 92.9064 42 Mo Molybdenum 95.94 43 Tc Technetium (98) 44 Ru Ruthenium. 1014)7 45* Rh 102-9O5S 'Pd •06 42 47 Ag iifcri I n > «6&2 48 Cd Cadmium 112X11 72 Hf Hafnium 178 49 73 Ta Tantalum 180.9479 74 W Tungsten 18334 75 Re Rhenium 186-20? 76 Os Osmium 190.23 77 Ir Iridium 192-217 78 Pt Piatinum 195078 79 Au Gold 196.9665 80 Hg Mercury 20039 104 Rf Rutherfordium 105 Db Dubmum 106 if,. 107 Bh Bohrlum 108 Hs Hassium 109 Mt Meitnerium 110 Ds Darmstadtium 111 Rg 112 Uub Ununblum (261) (262) (266) (264) (277) (268) (271) ' (272) (277) 57 La Lanthanum 138.9055 58 Ce Cenlum 140.116 59 Pr Jtaswdymlum 140.9077 60 Nd Neodymium 144,24 61 Pm Promethium (145) 62 Sm Samarium 150.36 63 Eu Europium 151.964 64 Gd Gadolinium 157.25 65 Tb Terbium 158.9253 89 Ac 90 Th 91 Pa 92 u 93 Np 94 Pu 95 Am 96 Cm 97 Bk Actinium 227.03 Thorium 232,0381 Proton.n.um 231.0359 Uranium 238.0289 Neptunium <237) Plutonium (244) Amerlcium (243) Curium (247) Berkelium (247) ¦ CD V^W & c Carbon 12.0107 ni Z>l AliH'i.Him 2tosvs Silicon 28.0655 31 Ga Gallium 69.723 Ge GctnUMum riM 49 In Indium 114318 50 Sn Tin 11871 81 TI 82 Pb Thallium 2043833 lead 207.2 > N fa c 9 F 10 Ne Nitrogen 14.0067 | Oxy Jfl I I5.S 94 Lu.iw is |P [16 s 17 CI 18 Ar Phosphorus 30.9738 Sulfur 32.065 Oiiorinc 35X53 39348 H /4921b 35 Br ¦Bromine W 79.904 36 Kr Krypton 83.798 51 Sb 52 Te 53 r1 54 Xe Antimony 121.76 Tellurium 127.6 Iodine 126.9045 Xenon 131.293 83 Bi 84 Po 85 At 86 Rn Bismuth 208-9804 Polonium 1 (209) Astatine 1210) Radon (222) ------- U.S. Environmental Protection Agency Office of Water (430 IT) Office of Science and Technology Health and Ecological Criteria Division 1200 Pennsylvania Avenue, NW Washington, DC 20460 EPA 822-R-21-002 i ------- Acknowledgments and Disclaimer The original Targeted National Sewage Sludge Survey (TNSSS) (USEPA, 2009a and 2009b) was made possible by the assistance and cooperation of numerous staff working at each of the sewage treatment facilities involved. The staffs of the facilities contacted during the course of TNSSS were, without exception, knowledgeable, friendly, helpful, and deservedly proud of their efforts to protect the environment and serve their local constituencies. This document summarizes the elemental analysis of archive samples from the TNSSS and has been reviewed and approved for publication online by the Office of Science and Technology. This report was prepared with the support of CSC, under the direction and review of the Office of Science and Technology. The report describes the sampling and analysis activities performed by CSC and its subcontractors under EPA Contract EP-C-05-045 in a follow-up to EPA's TNSSS and presents summary level data from the elemental analyses of sewage sludge samples. Neither the United States government, nor any of its employees, contractors, subcontractors, or other employees makes any warranty, expressed or implied, or assumes any legal liability or responsibility for any third party's use of, or the results of such use of, any information, apparatus, product, or process discussed in this report, or represents that its use by such a third party would not infringe on privately owned rights. Elemental Analysis of TNSSS Samples 11 April 2021 ------- [This page intentionally left blank] iii Elemental Analysis of TNSSS Samples April 2021 ------- Table of Contents Page Acknowledgments and Disclaimer ii Executive Summary 1 Section 1 Background and Organization 3 1.1 Background 3 1.2 Elemental Analyses 3 1.3 Content of this Report 3 Section 2 Study Objective and Design 4 2.1 Study Obj ective 4 2.2 Target Population 4 2.3 Stratification 5 2.4 Final Selection 5 Section 3 Sample Collection 8 3.1 Sample Collection 8 3.2 Representative Samples 9 3.3 Packing and Shipping Samples to the Repository 9 3.4 Storage and Shipments to Laboratories 10 Section 4 Sample Analyses 11 4.1 Parameters of Interest and Analytical Techniques 11 4.2 Laboratory 12 4.3 Analytical Challenges 12 Section 5 Data Review Procedures 14 5.1 General Review Procedures 14 5.2 QC Elements 14 5.3 Data Review Findings 16 Section 6 Study Results 17 6.1 Summary Results 17 6.2 Analytical Completeness 18 6.3 Analytical Sensitivity 18 6.4 Accounting for the Total Mass of Sewage Sludge 18 6.5 Comparison to Soil 19 Section 7 References 20 iv Elemental Analysis of TNSSS Samples April 2021 ------- Executive Summary This report describes the sampling and analysis activities performed in a follow-up to the Environmental Protection Agency's (EPA) Targeted National Sewage Sludge Survey (TNSSS) (USEPA, 2009a and USEPA, 2009b) and presents summary level data from the elemental analyses of sewage sludge samples. The Health and Ecological Criteria Division (HECD) and the Engineering and Analysis Division (EAD) within EPA's Office of Water, Office of Science and Technology, jointly conducted the original survey. The elemental analyses were conducted as a follow-up activity not associated with the original survey, but employing archived sewage sludge samples from the TNSSS for the analyses of specific elements. The objective of the analyses was to obtain data on the concentrations of specific elements and other measures of sewage sludge quality. One goal of the elemental analyses effort was to help further determine the makeup of sewage sludge (e.g., what macro constituents occur in sewage sludge). EPA was interested in determining what percentage of the total mass of the biosolids in the TNSSS specifically, and other biosolids in general, consists of the elements carbon, hydrogen, nitrogen, oxygen, sulfur, and silicon, as well as other major constituents. These results may be used to help further identify constituents of sewage sludge. The original survey sampling effort successfully collected sewage sludge from 74 randomly selected publicly owned treatment works (POTWs), or Water Resource Recovery Facilities (WRRFs), in 36 states. Sample collection began in late August 2006 and continued through late March 2007. Following collection of TNSSS samples that were analyzed for metals, anions, organics, brominated flame retardants, pharmaceuticals, steroids, and hormones, EPA archived additional samples at a sample repository in Baltimore, Maryland, where they were stored frozen for possible future use. In July 2009, 66 archive samples were submitted from the repository to a laboratory for elemental analyses. These 66 samples were selected based on the availability of materials in the archive and included samples from 62 facilities, as well as from four facilities that produce more than one type of final sewage sludge product. Elemental Analysis of TNSSS Samples 1 April 2021 ------- The results of the study are provided below. The results are provided as a summary of the results for the 66 TNSSS archive samples analyzed, listing the minimum, maximum, mean, and median results for each parameter. All sample results are reported in percent dry weight. Summary Results Parameter All Results in Weight Percent, on a Dry-Weight Basis Minimum Maximum Mean Median Carbon 12.90 46.31 31.17 31.39 Hydrogen 0.18 6.69 3.94 4.09 Nitrogen 1.15 7.94 3.84 3.97 Oxygen 5.17 29.27 19.64 20.43 Sulfur 0.13 4.05 1.32 1.18 TOC 10.39 45.27 29.93 30.77 TIC (calculated)* 0.00 7.45 1.37 1.02 Silica, Total 3.10 43.50 13.84 10.97 Siliconf 1.45 20.33 6.47 5.13 *ln instances where the TOC result was greater than or equal to the result for total carbon, the laboratory reported TIC as "TOC > TC." TIC was converted to 0.00 for the purposes of the survey. fThe results for silica (SiC>2) were converted to silicon (Si) by multiplying the silica result by 0.4675, which is the percentage by weight of Si in SiC>2. Elemental Analysis of TNSSS Samples 2 April 2021 ------- Section 1 Background and Organization 1.1 Background EPA conducted previous sewage sludge surveys. For example, EPA conducted a National Sewage Sludge Survey (NSSS) in 1988-1989 (USEPA, 1992 Volume I and II) to obtain unbiased national estimates of the concentrations of more than 400 pollutants in sewage sludge collected from 174 wastewater treatment plants that practiced at least secondary wastewater treatment. EPA conducted a second National Sewage Sludge Survey in 2001 (USEPA, 2001) to obtain updated national estimates of dioxins and dioxin-like compounds in sewage sludge managed by land application. EPA conducted a third survey, the Targeted National Sewage Sludge Survey (TNSSS) in 2009 (USEPA, 2009a and 2009b), to obtain updated concentration data for a group of pollutants that it identified for further evaluation and to support analyses of new and emerging contaminants, including pharmaceuticals, personal-care products, steroids, and hormones. As part of that effort, EPA archived additional samples from each of the facilities in the survey for possible future analyses. 1.2 Elemental Analyses Some of the archived material from the TNSSS was used to obtain data on the concentrations and support analyses of the elements carbon, hydrogen, oxygen, nitrogen, sulfur, and silicon, as well as other measures of sewage sludge quality (e.g., phosphrous, total organic carbon, and total, fixed, and volatile solids) that may be used to help further identify constituents of sewage sludge. These results help inform the quality of the elements in sewage sludge that may be land applied with the goal of improving soil quality and supporting plant growth. 1.3 Content of this Report Many details regarding study design and sampling can be found in the original TNSSS reports (USEPA, 2009a and USEPA, 2009b). This report focuses on the results from the elemental analyses of the TNSSS samples and presents summary level data relevant to the elemental analyses in the following topics: • Study Objective and Design • Sample Collection • Sample Analyses • Data Review Procedures • Study Results • References 3 Elemental Analysis of TNSSS Samples April 2021 ------- Section 2 Study Objective and Design 2.1 Study Objective The objective of the analyses was to obtain data on the concentrations of specific elements and other measures of sewage sludge quality as a follow-up to the Environmental Protection Agency's (EPA) Targeted National Sewage Sludge Survey (TNSSS) (USEPA 2009a and 2009b). The objective of the broader original TNSSS was to obtain national estimates of percentiles of concentrations for select pollutants in sewage sludge. EPA used a stratified random sampling design to select publicly owned treatment works (POTWs), or Water Resource Recovery Facilities (WRRFs), to be sampled. The target population and the selection process are briefly outlined below. Additional details regarding the survey design and the facility selection process are described in the TNSSS Sampling and Analysis Technical Report (USEPA, 2009a), as well as TNSSS Statistical Analysis Report (USEPA, 2009b). 2.2 Target Population EPA defined the target population for the TNSSS as WRRFs that met the following criteria: • Existed in 2002 or 2004 • Have flow rates greater than or equal to 1 million gallons per day (MGD) • Employ at least secondary treatment • Produce a final treated biosolid product • Are not known to employ a pond or lagoon as the final stage of treatment • Located in the contiguous United States Beginning with a national estimate of 16,255 WRRFs, EPA narrowed the list to 3,337 WRRFs that met the definition of the target population mentioned above that represented about 94% of the flow in the country. EPA originally selected a national sample of 80 WRRFs from that list of 3,337 facilities in the target population, using a stratified design. The final selection of facilities reduced the total number of facilities to 74 WRRFs in 36 states for the reasons described below. 4 Elemental Analysis of TNSSS Samples April 2021 ------- 2.3 Stratification EPA selected WRRFs using a random sampling design stratified for flow. EPA divided the 3,337 facilities into three categories, or strata, based on their design flow: • 1 to 10 MGD, representing approximately 75% of the WRRFs nationwide • 10 to 100 MGD, representing approximately 15% of the WRRFs nationwide • greater than 100 MGD, representing approximately 10% of the WRRFs nationwide After EPA determined the total number of facilities to be included in the study, EPA selected a proportionate number of WRRFs from each stratum at random. 2.4 Final Selection Figure 1 presents a map of the contiguous United States showing the approximate locations of the 80 WRRFs original randomly selected for this survey. The purpose of this figure is to illustrate the national scope of the survey. It does not indicate locations of specific wastewater discharges. 0 50100 200 300 400 Miles Figure 1. Geographic Distribution of 80 WRRFs Originally Selected for Sampling 5 Elemental Analysis of TNSSS Samples April 2021 ------- EPA sent each facility a formal written invitation, which was followed by a telephone call. These initial telephone contacts identified a small number of facilities that provided only partial treatment or were not of interest for this survey. Ultimately, EPA determined that samples would be collected at the 74 facilities listed in Table 2. As noted earlier, additional details on the facility selection process can be found in USEPA (2009a and 2009b). The 66 archived samples submitted for elemental analysis for this effort represent 62 of the 74 facilities in Table 2 (four of those 62 facilities produce more than one final product). The choice of the specific samples to be analyzed was based largely on the number and / or condition of containers remaining in the EPA sample archive. Not all of the original sample volume that had been sent to the laboratories for analyses of analytes for the original TNSSS effort, and that had been shipped back to be archived, was in good shape; some samples were broken in transit, lost in laboratory accidents, or where not used due to data quality concerns. Therefore, some samples were not suitable for elemental analysis. Samples from 12 facilities for which elemental analyses were not performed are shown at the end of Table 2. Table 2. 74 WRRFs Originally Sampled, by State and City Facility Name City State Sugar Creek WWTP Alexander City AL Aldridge Creek WWTP Huntsville AL Valley Sanitary District STP Indio CA San Francisco San Francisco CA El Estero WWTP Santa Barbara CA Santa Rosa Santa Rosa CA Stockton Water Quality Plant Stockton CA Los Angeles County Sanitation District Whittier CA Boulder WWTP Boulder CO South Windsor South Windsor CT Three Oaks WWTF Estero FL Orange County Northwest WRF Orlando FL Tampa Tampa FL Albany Albany GA Americus-Mill Creek Americus GA Boone STP Boone IA Calumet Water Reclamation Plant Chicago IL Plainfield WWTP Plainfield IL Lake County DPW, New Century STP Vernon Hills IL Blucher Poole WWTP Bloom ington IN William Ross Edwin WWTP Richmond IN Parsons Parsons KS Topeka Topeka KS Mayfield WWTP Mayfield KY Eunice Eunice LA Jefferson Parish East Bank WWTP Marrero LA Nantucket Nantucket MA Mechanic Falls Treatment Plant Mechanic Falls ME Benton Harbor-St. Joseph WWTP St. Joseph Ml Wixom WTP Wixom Ml Elizabeth City WWTP Elizabeth City NC Beatrice Beatrice NE Wildwood Lower WTF Cape May Court House NJ 6 Elemental Analysis of TNSSS Samples April 2021 ------- Facility Name City State Middlesex County Utility Authority WRC Sayreville NJ Verona TWP DPW Verona NJ Buffalo Buffalo NY Geneva A-C Marsh Creek STP Geneva NY North Tonawanda STP North Tonawanda NY Clermont County Commissioners Batavia OH Metropolitan Sewer District Little Miami WWTP Cincinnati OH Delaware County Alum Creek WWTP Delaware OH Mingo Junction STP Mingo Junction OH City of Klamath Falls WWTF Klamath Falls OR Western Westmoreland Municipal Authority Irwin PA Allegheny County sanitary Authority Pittsburgh PA Greater Pottsville Area Sewer Authority Pottsville PA Punxsutawyney Punxsutawney PA South Kingstown WWTF Narragansett Rl Plum Island WWTP Charleston SC Lawson Fork WTP Spartanburg SC Elizabethton Elizabethton TN Amarillo Amarillo TX Dallas Southside WWTP Dallas TX Trinity River Authority of Texas Ellis County TX Fredericksburg Fredericksburg TX Odo J. Riedel Regional WWTP Schertz TX Wagner Creek WWTP Texarkana TX Spanish Fork City Corporation Spanish Fork UT Buena Vista Buena Vista VA Beaver Dam Beaver Dam Wl El kins WWTP Elkins WV Huntington Huntington WV Facilities for which elemental analyses were not performed due to lack of archived material Phoenix WWTP Phoenix AZ Dupage County-Knollwood STP Wheaton IL Salisbury Salisbury MD Festus Crystal City STP Crystal City MO Hillsborough WWTP Hillsborough NC Canajoharie WWTP Canajohaire NY NYC DEP - Jamaica WPCP New York City NY Bedford Bedford OH Northeast Ohio Regional S D Southerly WWTP Cleveland OH Duncan Public Utilities Authority Duncan OK Tyler Southside WTP Tyler TX Everett City SVC Center MVD Everett WA Elemental Analysis of TNSSS Samples 7 April 2021 ------- Section 3 TNSSS Sample Collection 3.1 Sample Collection For the original TNSSS, EPA collected samples of the final sewage sludge product(s) produced at each of the 74 WRRFs. The TNSSS Sampling and Analysis Technical Report (USEPA, 2009a) describes the sample collection procedures in detail, which was revised periodically as needed during conduct of the survey. A summary of some of the sample collection procedures are provided below for the current effort to analyze for the target elements. EPA began sampling in August 2006 and completed sampling in March 2007. As described in the original TNSSS report, grab samples were taken using sampling equipment appropriate to the type of sewage sludge products produced (liquid or solid). Liquid samples were collected as free-flowing materials from storage tanks, transfer lines, taps, and hoses. After purging any lines used to collect samples, the liquid samples were placed directly into the final sample containers. If liquid sewage sludge was held in storage tanks, facility staff turned on mixing equipment in such tanks prior to sampling so that the collected liquids would be representative of the bulk product. Solid samples included dewatered sewage sludge collected from a belt press, filter press, drying bed, centrifuge, compost pile, or other source on site. Small grab samples were collected from multiple areas of any large piles, or multiple grabs from any continuous processes (e.g., belt press), so that samples were more likely to be representative of the bulk product. Several kilograms of material were collected and mixed for each final product. The person collecting the sample composited these small grabs in a large precleaned container of appropriate construction, mixed them well, and transferred the mixed material to the final sample containers. Any excess material remaining after all the sample containers had been filled was returned to the sewage sludge process. The grabs of solid samples ultimately used for the elemental analyses were collected with a large precleaned plastic serving spoon, mixed in a precleaned plastic wastebasket, and placed in high density polyethylene (HDPE) jars. Separate sampling equipment was used for each facility and all equipment was cleaned with a non-phosphate detergent, rinsed three times with tap water, and then reagent water prior to shipment to the facility. All containers used to sample sewage sludge for the TNSSS were purchased from commercial suppliers who provided certificates of analysis for common contaminants of interest (e.g., metals, semivolatile organics, pesticides, PCBs). The cleaning procedures applied by the vendors were presumed to be sufficient for the other analytes in the survey for which routine testing by the vendor was not performed. 8 Elemental Analysis of TNSSS Samples April 2021 ------- 3.2 Representative Samples Collecting materials during 2006 to 2007 for the TNSSS that were representative of the bulk sewage sludge product was more difficult at some facilities than at others. For example, at one facility that composted its final sewage sludge, samples were collected from one of the long piles of sewage sludge mixed with woods chips. The sampling piles measured approximately 50 feet long and over 6 feet high, with sides sloping up at roughly a 45 degree angle. Samples were collected from the oldest of the rows at facilities, which ranged from one to six months, depending on the season. The sampler exposed the materials by digging into the side of the pile at roughly six points along its length, on both sides of the pile, and a foot or more off the ground to avoid materials in contact with the concrete substrate. 3.3 Packing and Shipping Samples to the Repository After all the sample containers were filled and labeled, the sampler packed them for shipping, using procedures described in the sampling and analysis procedures (USEPA, 2009a). The sampler encased the glass jars in bubblewrap bags or layers of bubblewrap sheeting. The HDPE jars sometimes were placed in similar bags, or were packed with loose bubblewrap around them to prevent movement of the jars during shipping. Samples were packed into sturdy plastic ice chests. All of the samples from a given site were packed, with ice and bubblewrap, in either one 48-quart ice chest or two 28-quart ice chests, depending on availability. Ice was purchased near each facility and packaged in 1-gallon self-sealing plastic bags (in some cases, the facility provided ice). Approximately one pound of ice was used for each sample container (e.g., 4 bags containing 2 pounds of ice each were used to cool 8 samples in a 28-quart ice chest). Ice chests were shipped overnight from a full-service FedEx office to the sample repository operated by Microbac Laboratories in Baltimore, Maryland. Each sample shipment was tracked until receipt was confirmed at the repository. When samples arrived at Microbac, the repository staff inspected all the ice chests for external damage or leakage (none occurred). The repository staff did not measure the temperature of the cooler contents on receipt, but placed the samples in one of two walk-in freezers dedicated to EPA samples that were maintained at -11°C. Staff at the repository reported significant amounts of ice still present in the coolers, indicating that the samples were at or below appropriate temperature upon arrival. Elemental Analysis of TNSSS Samples 9 April 2021 ------- 3.4 Storage and Shipments to Laboratories The original TNSSS samples were stored frozen from the time of collection during 2006 to 2007 until early in July 2009 when 66 samples were shipped frozen from the EPA sample repository in Balitmore, MD to the elemental analysis laboratory (Columbia Analytical Services) for elemental analyses. The samples were shipped frozen, with large quantities of dry ice added to each cooler. Two shipments of two coolers each were sent to the elemental analysis laboratory. Despite the fact that one of the shipments was delayed a day en route by FedEx due to weather, all of the samples were received still frozen with visible dry ice remaining in each cooler. The cooler temperatures were recorded on receipt, and were -12°C or lower. Elemental Analysis of TNSSS Samples 10 April 2021 ------- Section 4 Sample Analyses 4.1 Parameters of Interest and Analytical Techniques The 11 parameters of interest for analysis are shown in Table 3, organized in four categories, along with the analytical techniques employed. Where formal methods exist, they are cited in the table; full citations are provided in USEPA (1996a, 1996b, 1997, 2001), ASTM (2005), and Kahn (1988). Table 3. Parameters of Interest Category Parameter Analytical Technique or Method Elements Total Carbon EPA Method 440: An aliquot of the air-dried and ground sample is combusted at 950°C, followed by detection of CO2, H2O, and N (after reduction of NOx) Hydrogen Nitrogen Oxygen Modified EPA Method 440: An aliquot of the air-dried and ground sample is heated in a graphite pyrolysis furnace at 1300°C, converting the oxygen to CO2, which is measured by infra-red detection. This modified method employs an oxygen analyzer module designed specifically for this purpose by the manufacturer Sulfur ASTM Method D4239: An aliquot of the air-dried and ground sample is combusted at 1350°C, followed by infra-red detection of SOx Forms of Carbon Total organic carbon (TOC) SW-846 Method 9060, as modified by Lloyd Kahn (EPA Region 2): An aliquot of the air-dried and ground sample is pre-treated with HCI to remove inorganic carbon. The sample is combusted at 1350°C, followed by infra-red detection of CO2 Total inorganic carbon (TIC) TIC is a calculated value, as total carbon minus TOC Solids Percent solids (total solids) An appropriate size aliquot is air dried at 30-40°C until approximately 95% dry. The air dry loss is determined gravimetrically and the air-dried sample is ground to < 60 mesh. The ground sample is further dried at 105°C and analyzed gravimetrically for residual moisture. The percent solids are determined based on the overall loss of weight during both drying steps Volatile solids EPA Method 1684: An aliquot of the sample is heated to 550°C and the volatile solids are determined gravimetrically, as the material lost at 550°C. Volatile solids are reported as the percentage of the total solids that they represent Fixed solids EPA Method 1684: The fixed solids are determined gravimetrically, as the material that remains after heating the sample to 550°C. Fixed solids are reported as the percentage of the total solids that they represent Metal Silicon (as silica, SiCh) SW-846 Methods 3052 (digestion) and 6010 (analysis): An aliquot of the air-dried and ground sample is digested with HNO3 and H2O2 in a PTFE vessel, followed by digestion with HF and HCI. Excess HF is neutralized with boric acid. This procedure results in the complete dissolution of the sample. The digestate is analyzed by inductively coupled plasma (ICP) optical emission spectroscopy 11 Elemental Analysis of TNSSS Samples April 2021 ------- 4.2 Laboratory As with the earlier portions of the TNSSS, EPA prepared for this effort a study-specific statement of work (SOW) for the elemental analyses and competitively solicited bids from multiple laboratories. EPA awarded the contract for the elemental analyses to Columbia Analytical Services, Inc., in Tucson, Arizona. 4.3 Analytical Challenges From an analytical standpoint, sewage sludge is a challenging matrix with which to work. The concentrations of pollutants present in a given sample can vary widely, depending on the nature of the inputs to the treatment plant (e.g., domestic or industrial), and sewage sludge contains other components that are potential interferences in the analyses of the pollutants of interest. These interferences can manifest themselves at all stages of the analytical process, from sample preparation through the final determinative analysis. Fortunately, the elemental analyses described in this report involved fewer challenges. For example, the elements of interest are present in substantial quantities in sewage sludge and analytical sensitivity was never an issue and "nondetects" were not a concern. The one substantive problem encountered by the laboratory involved air drying the samples prior to analysis. Some of the samples were liquid that contained large amounts of water (up to 99%). Even though only a few grams of sample were required for the various analyses, wet samples were slow to dry at 30 to 40°C. In addition, some WRRFs treat wastewater with chemical thickeners during production or with lime (calcium carbonate) prior to use or disposal. These treatment agents can cause the sewage sludge to retain moisture and may make it more difficult to air dry the samples. The laboratory reported that some samples required as much as two weeks to air dry, compared to a more typical two days for other solid matrices such as soils. In response, the laboratory made minor changes to their sample preparation procedures, including using larger plastic drying trays for some samples. The larger tray surface allowed the sample to be spread in a thinner layer for air drying. The laboratory also reported minor QC problems during the oxygen analyses. They obtained higher than expected results for some calibration verification standards analyzed at the end of a batch of sewage sludge samples. The calibration verification standards are QC samples used to ensure that the instrumentation is under control during the analyses of the field samples. Based on other QC measures, they believe that the problem was a function of some component of the sewage sludge matrix itself that affected the instrument over time. They overcame the problem by reducing the number of samples in each analysis batch, thereby increasing the frequency at which the calibration verifications were analyzed. Using this approach, the laboratory was able to meet the acceptance criteria for the calibration verification standards, thus demonstrating that the instrumentation was in control for each smaller batch of field sample analyses. 12 Elemental Analysis of TNSSS Samples April 2021 ------- The total inorganic carbon (TIC) is determined as the difference between the results from the separate analyses of total carbon and total organic carbon (TOC). In an organic-rich matrix, such as sewage sludge, most or all of the carbon may be present as organic carbon. Given the separate potential uncertainties in the measurements of total carbon and TOC, there were a few instances in which the calculated TIC result was zero or a negative number. In these instances, the laboratory reported the results as "TOC > TC." Elemental Analysis of TNSSS Samples 13 April 2021 ------- Section 5 Data Review Procedures 5.1 General Review Procedures EPA subjected every laboratory data package submitted under this study to a comprehensive review for data completeness and compliance with project and method specifications and subcontract requirements to ensure that the data met the objectives of the study. Trained staff performed these reviews and identified and corrected data deficiencies as early as possible to maximize the amount of usable data generated during the study. 5.2 QC Elements As noted in Section 4, the elemental analyses and other analyses in this phase of the survey are simpler than many of the analyses conducted earlier (USEPA, 2009a and 2009b), and presented fewer analytical challenges. Another advantage for these elemental analyses is that well-characterized reference materials are available for the majority of the parameters that can be used as quality control (QC) checks. Table 4 lists the QC elements and acceptance criteria that the laboratory employed for each of the analysis types. Elemental Analysis of TNSSS Samples 14 April 2021 ------- Table 4. QC Elements Parameter Category Method QC Element Acceptance Limit Total Carbon EPA Method 440 Method blank LCS1 using S-benzyl thiuronium or phenacetin Sewage sludge reference material CN 1702 Duplicate sample analysis Blank <0.01 wt.% Hydrogen EPA Method 440 LCS Recovery 95-105% RM2 Recovery 90-110% RPD3 of duplicates Elements Nitrogen EPA Method 440 <10% Oxygen Method blank Blank <0.01 wt.% EPA Method LCS using benzoic acid or acetanilide LCS Recovery 95-105% 440 (modified) Duplicate sample analysis RPD of duplicates <20% Sulfur ASTM D4239 Method blank Coal reference material AR2776 run in replicate Sewage sludge reference material CN 1702 Duplicate sample analysis Blank <0.01 wt.% RM Recovery 90-110% RPD of duplicates <20% Forms of Carbon Total organic Method blank Blank <0.01 wt.% carbon (TOC) SW-846 9060 Coal reference material AR2781 run in replicate Duplicate sample analysis RM Recovery 90-110% RPD of duplicates <20% Total solids EPA Method 1684 Volatile solids Method blank Blank <0.01 wt.% Solids EPA Method Rice flour reference material AR2028 run in replicate RM Recovery 85-115% 1684 Duplicate sample analysis RPD of duplicates <20% Fixed solids EPA Method 1684 Silicon (as Method blank Blank <0.01 wt.% Metal silica, Si02) NIST SRM 2710 Montana soil RM Recovery 85-115% SW-846 6010 Duplicate sample analysis RPD of duplicates <20% 1 LCS = Laboratory control sample 2 RM = Reference material (may be a NIST Standard Reference Material®, or a certified reference material from another source) 3RPD = Relative percent difference Because a reference material for oxygen was not readily available, the laboratory employed two laboratory control samples (LCS) analyses, one prepared from benzoic acid and a second one prepared from acetanilide were utilized. Conversely, because two reference materials were available for the sulfur analyses, no LCS was employed for that analysis. An LCS was not employed for the TOC analyses. 15 Elemental Analysis of TNSSS Samples April 2021 ------- Since total inorganic carbon (TIC) is a calculated value, there are no QC elements exclusive to this parameter. Rather, the quality of the TIC results is dependant on the QC associated with the total carbon and total organic carbon measurements. 5.3 Data Review Findings The data review efforts did not identify any substantive issues with the quality of the analytical results for the elemental analyses. As noted earlier, the laboratory reran some samples because of issues they identified during their internal reviews. The availability of applicable reference materials for these analyses also aided in ensuring data quality. We did identify a small number of data reporting errors and inconsistencies, including a few instances of transposed results and spreadsheet cells formatted as text instead of numbers. These issues were found in the electronic data during efforts to compile the data from several electronic data deliverables into a single file of the study results. EPA examined the corresponding hard copy results, contacted the laboratory to confirm the errors, and requested that the laboratory submit corrected data. The few errors and consistencies that we identified were readily resolved by working with the laboratory. Elemental Analysis of TNSSS Samples 16 April 2021 ------- Section 6 Study Results 6.1 Summary Results Table 5 provides a summary of the results for the 66 TNSSS archive samples analyzed, listing the minimum, maximum, mean, and median results for each parameter. All sample results are reported in percent dry weight. Table 5. Summary Results Parameter All Results in Weight Percent, on a Dry-Weight Basis Minimum Maximum Mean Median Carbon 12.90 46.31 31.17 31.39 Hydrogen 0.18 6.69 3.94 4.09 Nitrogen 1.15 7.94 3.84 3.97 Oxygen 5.17 29.27 19.64 20.43 Sulfur 0.13 4.05 1.32 1.18 TOC 10.39 45.27 29.93 30.77 TIC (calculated)* 0.00 7.45 1.37 1.02 Silica, Total 3.10 43.50 13.84 10.97 Siliconf 1.45 20.33 6.47 5.13 *ln instances where the TOC result was greater than or equal to the result for total carbon, the laboratory reported TIC as "TOC > TC." TIC was converted to 0.00 for the purposes of the survey. fThe results for silica (SiC>2) were converted to silicon (Si) by multiplying the silica result by 0.4675, which is the percentage by weight of Si in SiC>2. Table 6 provides a similar summary of the results for total solids, volatile solids and fixed solids for the 66 samples. The results for the total solids are reported as percent dry weight. The fixed and volatile solids are calculated as a percentage of the total solids content. In addition, because the fixed solids and volatile solids are complementary to one another (e.g., volatile solids represent the material lost when the sample is heated to 550°C, while fixed solids represents the material that remains), the minimum/maximum value for the fixed solids and the minimum/maximum value for volatile solids do not occur in the same sample. Table 6. Summary Results for Solids Parameter All Results in Percent, on a Dry-Weight Basis Minimum Maximum Mean Median Total Solids (weight percent) 0.49 88.43 22.72 18.23 Volatile Solids (as percentage of total solids) 16.87 83.80 56.56 59.14 Fixed Solids (as percentage of total solids) 16.20 83.13 43.44 40.87 17 Elemental Analysis of TNSSS Samples April 2021 ------- 6.2 Analytical Completeness "Completeness" is a quality assurance measure of the number of samples collected and analyzed compared to the number of useable results. All of the results for this elemental analysis study met the acceptance criteria in the applicable analytical methods and the laboratory provided usable results for every sample submitted for analysis. Thus, analytical completeness is 100% for the overall effort. 6.3 Analytical Sensitivity EPA did not expect that sensitivity would be a concern for the elemental and other analyses in this portion of the survey; all sewage sludge contains the elements of interest and all sewage sludge contains solids. The laboratory routinely air dries and grinds all samples prior to analysis and the elements of interest are not lost during drying. The only instances of "nondetects" occurred for the total inorganic carbon (TIC). In ten samples, the results for total organic carbon (TOC) were greater than or equal to the results for total carbon (TC), and the calculated TIC was a negative number. EPA examined the ten cases where this occurred. In 7 cases the percent difference between the TC result and the TOC result was less than or equal to 2%. Thus, even a 1% uncertainty in each of the two measurements might have caused the TOC to exceed the total carbon result. The remaining three cases involved percent differences between 6 and 15%, all within reasonable uncertainty estimates for the two measured values involved in the calculation. Because negative values for the TIC have no physical meaning, all ten of those TIC results were set to 0.00 for the purposes of the reporting results from this study. 6.4 Accounting for the Total Mass of Sewage Sludge One goal of the elemental analyses effort was to help further determine the makeup of sewage sludge. EPA was interested in determining what percentage of the total mass of the biosolids in the TNSSS specifically, and in sewage sludge in general, consisted of the elements carbon, hydrogen, nitrogen, oxygen, sulfur, and silicon, as well as other major constituents (e.g., phosphorus, total organic carbon, and total, fixed, and volatile solids). Table 7 provides information on the percent makeup for two elemental combinations of treated sewage sludge. Table 7. Percent of Sample Mass Comprised of Selected Elements C,N,H,0,S, and Si only C,N,H,0,S, Si, plus AI,Ca,Fe,Mg,P, and Na Minimum (%) 36.83 52.30 Maximum (%) 86.39 94.55 Mean (%) 66.37 77.37 Median (%) 66.52 80.42 18 Elemental Analysis of TNSSS Samples April 2021 ------- On average across all 66 samples, we can account for approximately 66.4% and 77.4% of the mass of the sewage sludge, respectively, using these two groups of analytes from Table 7. Using all 12 analytes, we can account for almost 95% of the mass of one sample (i.e., maximum %) and over 50% of all other samples. 6.5 Comparison to Background Soil Concentrations Finally, we compared the results for the sewage sludge samples in this study to data for soils in the U.S. Table 8 compares the mean and median results from this study to data for typical soils (A Horizon) from the U.S. Geological Survey (Smith et al., 2013). The U.S. Geological study sampled 4,857 sites for various geochemical and mineralogical elements and minerals in soils of the conterminous United States. Table 8. Comparison of Sewage Sludge to Soil Elemental Concentrations Element Sewage Sludge Mean % Sewage Sludge Median % Soil Mean % Soil Median % TIC 1.37 1.02 0.30 0.60 TOC 29.93 30.77 2.75 1.55 O 19.64 20.43 — — Si 6.47 5.13 — ... Ca 4.46 2.75 1.61 0.74 H 3.94 4.09 — ... N 3.84 3.97 — ... Fe 2.39 1.42 2.19 1.99 P 2.07 1.76 0.06 0.05 S 1.32 1.18 0.06 0.03 Al 1.29 1.10 4.65 4.71 Based on the comparative data in Table 8, it can be seen that sewage sludge can be a source of essential plant nutrients. Nutrients such as calcium, nitrogen, phosphorus and sulfur are all essential plant nutrients which are low in soils and sewage sludge can provide an adequate supply for plant growth. Any land application of sewage sludge should follow the pollutant limits and other regulations set forth in 40 CFR Part 503. 19 Elemental Analysis of TNSSS Samples April 2021 ------- Section 7 References Kahn, Lloyd, 1988. USEPA Region II, Determination of Total Organic Carbon in Sediment, July 1988. McQuaker, N. R., and M. Gurney, 1977. Determination of total fluoride in soil and vegetation using an alkali fusion-selective electrode technique. Analytical Chemistry. 49(l):53-56 Schacklette, H.T., and J.G. Boeragen, 1984. Element Concentrations in Soil and Other Surficial Materials of the Conterminous United States, USGS Professional Paper 1270. https://pubs.usgs.gov/pp/1270/. Smith, D.B., W.F. Cannon, L.G. Woodruff, F. Solano, J.E. Kilburn, and D.L. Fey, 2013. Geochemical and mineral ogical data for soils of the conterminous United States: U.S. Geological Survey Data Series 801, 19 p., https://pubs.usgs.gov/ds/801/. USEPA, 1992. Statistical Support Documentation for the 40 CFR, Part 503 Final Standards for the Use or Disposal of Sewage Sludge. Volume I. Final Report November 11, 1992. https://www.epa.gov/sites/production/files/2015- 04/documents/statistics 1992 support document - biosolids vol i.pdf USEPA, 1992. Statistical Support Documentation for the 40 CFR, Part 503 Final Standards for the Use or Disposal of Sewage Sludge. Volume II. Final Report November 11, 1992. https://www.epa.gov/sites/production/files/2Q15- 04/documents/statistics 1992 support document - biosolids vol ii.pdf USEPA, 1996a. SW-846 Method 3052, Microwave Assisted Acid Digestion of Siliceous and Organically Based Matrices, December 1996. https://www.epa.gov/sites/production/files/2015-12/documents/3052.pdf. USEPA, 1996b. SW-846 Method 6010B, Inductively Coupled Plasma-Atomic Emission Spectrometry, December 1996. USEPA, 1997. Method 440.0, Determination of Carbon and Nitrogen in Sediments and Particulates of Estuarine/Coastal Waters Using Elemental Analysis, National Exposure Research Laboratory Office of Research and Development, Cincinnati, OH, September 1997. https://cfpub.epa.gov/si/si public record report.cfm?Lab=NERL&dirEntryId=309418. USEPA, 2001. Method 1684, Total, Fixed, and Volatile Solids in Water, Solids, and Biosolids, Office of Water, January 2001, EPA-821-R-01-015. https://www.epa.gov/sites/production/files/2015-10/documents/method 1684 draft 2001.pdf. 20 Elemental Analysis of TNSSS Samples April 2021 ------- USEPA, 2002. Statistical Support Document for the Development of Round 2 Biosolids Use or Disposal Regulations. April 2002; EPA -822-R-02-034. https://www.epa.gov/sites/production/files/2018-ll/documents/statistical-support-doc-round2- biosolids.pdf. USEPA, 2009a. Targeted National Sewage Sludge Survey Sampling and Analysis Technical Report, January 2009, EPA-822-R-08-016. https://www.epa.gov/sites/production/files/2018-ll/ documents/tnsss-sampling-anaylsis-tech-report.pdf. USEPA, 2009b. Targeted National Sewage Sludge Survey Statistical Analysis Report, April 2009, EPA-822-R-08-018. https://www.epa.gov/sites/production/files/2021-02/documents/tnsss- statistical-analysis-report.pdf. 21 Elemental Analysis of TNSSS Samples April 2021 ------- |