28 —Chopter 2 Tonsttvens in Wostewotor 27 2-8 2-9 Total and Soluble Chemical Oxygen Demand (COD and SCOD) 93 Total and Dissolved Organic Carbon (TOC and DTOC) 94 UV-Absorbing Organic Constituents 95 Theoretical Oxygen Demand (ThOD) 96 Interrelationships between BOD; COD, and TOC 96 Oil and Grease 98 Surfactants 98 INDIVIDUAL ORGANIC COMPOUNDS 99 Priority Pollutants 99 Analysis of Individual Organic Compounds 100 Volatile Organic Compounds (VOCs) 100 Disinfection Byproducls 102 Pesticides and Agricultural Chemicals 102 Emerging Organic Compounds 102 BIOLOGICAL CHARACTERISTICS 104 Microorganisms Found in Surface Waters and Wastewater 104 Pathogenic Organisms 109 Use of Indicator Organisms 115 Enumeration and Identification of Bacteria 118 Enumeration and Identification of Viruses 126 Polymerase Chain Reaction (PCR) 129 Development of Microorganisms Typing Techniques © 130 New and Reemerging Microorganisms 130 TOXICITY TESTS 130 Toxicity:Terminology 131 Toxicity Testing 133 Analysis of Toxicity Test Results 134 Application of Toxicity Test Resulls 136 Identification of Toxicity Components 137 PROBLEMS AND DISCUSSION TOPICS 139 REFERENCES 148 An understanding of the nature of wastewater is essential in the design and operation of collection, treatment, and reuse facilities, and in the engineering management of envi- ronmental quality. To promote this understanding, the information in this chapter is pre- sented in nine sections dealing with (1) an introduction to the constituents found in ‘wastewater, (2) sampling and analytical procedures, (3) physical characteristics, (4) inor- ganic nonmetallic constituents, (5) metallic constituents, (6) aggregate organic con- stituents, (7) individual organic constituents and compounds, (8) biological character- istics, and (9) toxicity tests. The material in this chapter has been organized in a manner similar to that used in Standard Methods (1998), the standard reference work for the characterization of wastewater in the field of environmental engineering.2-2 242 Sampling and Analytical Procedures. 29 ‘WASTEWATER CONSTITUENTS ‘The physical, chemical, and biological constituents found in wastewater and the con- stituents of concern in wastewater are introduced briefly in the following discussion. Constituents Found in Wastewater Wastewater is characterized in terms of its physical, chemical, and biological composi- tion. The principal physical properties and the chemical and biological constituents of wastewater, and their sources, are reported in Table 2-1. It should be noted that many of the physical properties and chemical and biological characteristics listed in Table 2-1 are interrelated. For example, temperature, a physical property, affects both the amounts of gases dissolved in the wastewater and the biological activity in the wastewater. Constituents of Concern in Wastewater Treatment ‘The important constituents of concem in wastewater treatment are listed in Table 2-2. Secondary treatment standards for wastewater are concemed with the removal of biodegradable organics, total suspended solids, and pathogens. Many of the more strin- gent standards that have been developed recently deal with the removal of nutrients, heavy metals, and priority pollutants. When wastewater is to be reused, standards nor- mally include additional requirements for the removal of refractory organics, heavy metals, and in some cases, dissolved inorganic solids. SAMPLING AND ANALYTICAL PROCEDURES Proper sampling and analytical techniques are of fundamental importance in the char- acterization of wastewater. Sampling techniques, the methods of analysis, the units of measurement for chemical constituents, and some useful concepts from chemistry are considered below. ‘Sampling ‘Sampling programs are undertaken for a variety of reasons such as to obtain (1) routine operating data on overall plant performance, (2) data that can be used to document the performance of a given treatment operation or process, (3) data that can be used to iplement proposed new programs, and (4) data needed for reporting regulatory com- pliance. To meet the goals of the sampling program, the data collected must be: 1. Representative. The data must represent the wastewater or environment being sampled, 2. Reproducible. The data obtained must be reproducible by others following the same sampling and analytical protocols. 3. Defensible. Documentation must be available to validate the sampling proce- dures. The data must have a known degree of accuracy and precision, 4, Useful. The data can be used to meet the objectives of the monitoring plan (Pep- per etal., 1996) Because the data from the analysis of the samples will ultimately serve as a basis for implementing wastewater management facilities and programs, the techniques used in ‘a wastewater sampling program must be such that representative samples are obtained.30 Chopter 2 Constituents in Wastewoter Table 2-1 ‘Common analyses used to assess the constituents found in wastewater? Physical characteristics Toa! solids 1s Teal volatile solids Vs Total fixed solids TFs, Tota suspended solids TSS Velie suspended vss Fixed suspended solids FSS Total dissolved solids TDs {Ts ~ TSS) Volatile dissolved solids VDS. Toll fixed dissolved FDS solids Setleabe solids Parfcle size disribuion PSD Tutbidiy NTU: Calor light brown, gray, block Transmittance “T Odor TON! Temperature Cor 'F Density ’ Conductivity Ec Inorganic chemical characteristics Free ammonia NAY Organie nitrogen OrgN Total Kjeldahl nitrogen TKN (Org N+ NH) Nitites NOs Nitrates NOS Total nitrogen 1N Inorganic phosphorus, Inorg P Total phosphorus id ‘Organic phosphorus Org P To ossess the reuse potential of @ wastewater and to determine the most suitable ype of operations and processes for its treatment To determine those solids that wil setle by gravity in a ‘paced tne pred eae To assess the performance of Kreatment processes Used to assess the quality of realed wastewater To assess the condition of wastewater (resh or septic) Used to assess the suitability of treated effluent for UV disinfection To determine if edors will bea problem Important in the design and operation of biological processes in trecimentfociliies Used to assess the suitability of treated effivent for cgriculvral applications Used as « measure of the nutients present end the degree cof decomposition in the wastewater; the oxidized forms con be token as a measure of the degree of oxidation (continued)| Table 2-1 (Continued) Abbreviation/ Test definition Inorganic chemical characteristics (continued) pH pH = —log (H+) Alkalinity EHCO; + CO;? + OH HH Chloride a Sulfate s0;? Metals As, Cd, Ca, Cr, Co, Cu, Pb, Mg, Hg, Mo, Ni Se, Na, Za Specific inorganic elements compounds Vorious gases Op, CO, NHy, HS, CH, Organic chemical charact Five-day carbonaceous CBOD, biochemical oxygen demand Ultimate carbonaceous BOD (ls0 BOD, 8OD,) biochemical exygen demand Nitrogenous oxygen NOD demand Chemical oxygen cop demand Totol organic carbon Toc Specific organic MBAS®, CTAS! compounds and classes cof compounds Biological characteristics Coliform organisms MEN (ot probable number) Specific microorganisms Bacteria, protoz00, me s helminth, viruses Toxicity TU, ond TU, 2-2 Sampling ond Analytical Procedures 31 ‘A measure of the acidity or basicity of an aqueous solution ‘A measure of the buffering capacity ofthe wastewater To ossess the suitbilty of wastewater for agricultural reuse ‘To ossess the potential forthe formation of odors and may imped the treatobility of the waste sludge To assess the sutobilly ofthe wastewater for reuse and for toxicity efecs in treatment. Trace amounts of metals ‘are important in biological treatment To assess presence or absence ofa specific consfivent The presence or absence of specific gases ‘A measure ofthe amount of oxygen required to stabilize ‘a woste biologically ‘A measure ofthe amount of oxygen required to stobilize a woste biologically ‘A measure of the amount of oxygen required 1 oxidize biclogcally the nitrogen in the wasteweter Yo nitrate Often used os o substitute for the BOD test (Often used as @ substitute for the BOD test To determine presence of specific organic compounds ‘ond to essess wheter spocel design measures wl be ‘needed for removal To assess presence of pathogenic bacteria and efiocvonees of disinfcton process To assess presence of specific ergonisms in connection with plant operation and for reuse Toxic unit acute, Toxic unit chronic Adapted, in pon, rom Crites and Tchobonoglous (1998} "Details on the vorious tests, may be found in Standard Methods (1998), "NTU = nephelometic turbidity unit STON «= threshold odor number “MBAS = methylene blue active substances ICTAS = cobalt thiocyonate active substances32 Chapter 2 Constivents in Wastewater Table 2-2 Principal constituents of concern in ‘wastewater treatment Constituent Reason for importance ‘Suspended solids Suspended solids can lead to the development of sl deposits cromrsbic codices when vnreted woxovaiets achorged inthe aquatic environment Biodegradable organics Composed principally of proteins, corbohydtes, nd fl, arr Li are Ge ntesaad ety camry ties cf8OD (biochemical onygen demand) and COD (chemical ‘oxygen demand). If discharged untreated to the environment, their biological stabilization can lead to the depletion of natural ‘oxygen resources and to the development of septic condiions Pathogens ‘Communicable diseases con be transmitted by the pothogenic organisms that may be present in wastewaler Nutrients Both nitrogen and phosphorus, along with corbon, are essential nutrients for grow, ‘thon di lischorged to the aquatic ervronment, these nutrients can lead fo the growth of tndesrble aquatic fe, When discharged in excessive amounts ‘on land, they con also lead to the pollution of groundwater Priority polltons rgnic a nroni xno dd on he oi fir wn or suspected carcinogenic, motogentiy, kralogenily, Shah cases Neve acelin rostoveater Refractory organics ‘These organics tend to resist conventional methods of ‘wostwaor reament Typical examples incade surfactants, penal, and agricola pesticides Heowy metals Heawy metal ore usvlly added fo wasewete from Commercial ond instil ocviles and may hove to be removed f the waslewater sto be revsed Dissoled inorganics _Ingrganc costivens such os cokium, sodium, and sulfate ore cedded tothe eviginal domestic weer soppy os rea of water use ond me hoe fo be removed te wasters tobe There are no universal procedures for sampling; sampling programs must be tailored individually to fit each situation (see Fig. 2-1). Special procedures are necessary to handle sampling problems that arise when wastes vary considerably in composition Before a sampling program is undertaken, a detailed sampling protocol must be developed along with a quality assurance project plan (QAPP) (known previously as quality assurance/quality control, QA/QC). As a minimum, the following items must be specified in the QAPP (Pepper et al., 1996). Additional details on the subject of sam- pling may be found in Standard Methods (1998). 1. Sampling plan. Number of sampling locations, numbet (see homework problem 2-5) and type of samples, time intervals (e.g., real-time and/or time-delayed samples). 2. Sample types and size. Catch or grab samples, composite samples, or integrated samples, separate samples for different analyses (¢.g., for metals). Sample size Ge, volume) requiredFigure 2-1 Collection of somples for enclysis:(o} collection of an effluent sample from «© pilot plan! reolment unit and (6) view of on uncapped monitoring well equipped with sompling outlets forfour diferent well depths Samples ave collected from each depth to monitor a groundwater injection system 2-2 Sampling and Anclyicol Procedures 33 3. Sample labeling and chain of custody. Sample labels, sample seals, field log book, chain of custody record, sample analysis request sheets, sample delivery to the laboratory, receipt and logging of sample, and assignment of sample for analysis, 4. Sampling methods. Specific techniques and equipment to be used (e.g., manual, automatic, or sorbent sampling). 5. Sampling storage and preservation. Type of containers (e.g., glass or plastic), preservation methods, maximum allowable holding times. 6. Sample constituents. A list of the parameters to be measured. 7. Analytical methods. A list of the field and laboratory test methods and procedures to be used, and the detection limits for the individual methods. If the physical, chemical, and/or biological integrity of the samples is not main- tained during interim periods between sample collection and sample analysis, a carefully performed sampling program will become worthless. Considerable research on the prob- lem of sample preservation has failed to perfect a universal treatment or method, or to formulate a set of fixed rules applicable to samples of all types. Prompt analysis is undoubtedly the most positive assurance against error due to sample deterioration. When analytical and testing conditions dictate a lag between collection and analysis, such as when a 24-h composite sample is collected, provisions must be made for preserving sam- ples (see Fig. 2-2). Current methods of sample preservation for the analysis of proper- ties subject to deterioration must be used (Standard Methods, 1998). Probable errors due to deterioration of the sample should be noted in reporting analytical data,94 Chapter 2 Constivents in Wastewater Figure 2-2 Typical ovtomatic composite sompler used to collect ond ‘erigercte somples over @ 24h period. Methods of Analysis The analyses used to characterize wastewater vary from precise quantitative chemical determinations to the more qualitative biological and physical determinations. The quantitative methods of analysis are either gravimetric, volumetric, or physicochemical In the physicochemical methods, properties other than mass or volume are measured. Instrumental methods of analysis such as turbidimetry, colorimetry, potentiometry, polarography, adsorption spectrometry, fluorometry, spectroscopy, and nuclear radia- tion are representative of the physicochemical analyses. Details concerning the various analyses may be found in Standard Methods (1998), the accepted reference that details the conduct of water and wastewater analyses. Regardless of the method of analysis used, the detection level must be specified Several detection limits are defined and are listed below in order of increasing levels (Standard Methods, 1998). 1. Instrumental detection level (IDL). Constituent concentration that produces a sig- nal greater than five times the signal/noise ratio of the instrument. The IDL is, many respects, similar to “critical level” and “criterion of detection.” The latter level is stated as 1.645 times the standard deviation s of blank analyses. 2. Lower level of detection (LLD). Constituent concentration in reagent water that produces a signal (2 X 1.6455) above the mean of blank analyses, where s is the standard deviation. The value at 2 1.645s sets both Type I and Type II errors at 5 percent. Type I and Type Il errors are used to test the null hypothesis (Larson2-2 Sompling and Anolyfcal Procedures, 35, and Farber, 2000). Other names for this level are “detection level” and “level of detection” (LOD). 3. Method detection level (MDL). Constituent concentration that, when processed through the complete method, produces a signal with a 99 percent probability that it is different from the blank. For seven replicates of the sample, the mean must. be 3.14s above the blank, where s is the standard deviation of the seven replicates. Compute MDL from replicate measurements one to five times the actual MDL. ‘The MDL will be larger than the LLD because of the few replications and the sample processing steps, and may vary with constituent and matrix. 4. Level of quantification (LOQ). Constituent concentration that produces a signal sufficiently greater than the blank that can be detected within specified levels by good laboratories during routine operating conditions. Typically it is the concen- tration that produces a signal 10s above the reagent blank signal Units of Measurement for Physical and Chemical Parameters The results of the analysis of wastewater samples are expressed in terms of physical and chemical units of measurement. The most common units for these measurements are reported in Table 2-3. Measurements of chemical parameters are usually expressed in the physical unit of milligrams per liter (mg/L) or grams per cubic meter (g/m®). The concentration of trace constituents is usually expressed as micrograms per liter (yig/L) or nanograms per liter (ng/L). ‘As noted in Table 2-3, the concentration can also be expressed as parts per million (ppm), which is a mass-to-mass ratio. The relationship between mg/L and ppm Hy mg/L © specific gravity of fluid ppm (2-1) For dilute systems, such as those encountered in natural waters and wastewater, in which cone liter of sample weighs approximately one kilogram, the units of mg/L or g/m? are interchangeable with ppm. The terms “parts per billion” (ppb) and “parts per trillion” (ppt) are used interchangeably with j.g/L and ng/L, respectively. Dissolved gases, con- sidered to be chemical constituents, are expressed in parts per million by volume (ppm,), 4g/m?, or mg/L. Conversion of gas concentrations between ppm, and g/m is given by Eq. (2-44), the universal gas law. Gases that evolve as byproducts of waste- water treatment, such as carbon dioxide and methane (from anaerobic decomposition), are measured in terms of L or m? (ft?). Parameters such as temperature, odor, hydrogen ion, and biological organisms are expressed in other units, as explained below. Useful Chemical Relationships Other useful relationships from chemistry used in the analysis and evaluation of waste- water test results and in the design 6f treatment facilities include mole fraction, elec troneutrality, chemical equilibrium, activity coefficient, ionic strength, and solubility product. Mole Fraction. The ratio of the number of moles of a given solute to the total num- ber of moles of all components in solution is defined as the mole fraction. Along with