2-5 METALLIC CONSTITUENTS

Trace quantities of many metals, such as cadmium (cd), chromium (cr), copper (Cu), Iron (Fe,
lead (Pb), manganese (Mn), mercury (Hg), nikel (Ni), and zine (Zn) are important cosituent of
most water,many of these metals are necessary for growth of biological life, and absence of
sufficient quantities of them could limit growth of algae, for example. The presence of any of
these metals in excessive quantities will interfere with many beneficial uses of the water because
of their toxicity; therefore, it is frequently desirable to measure and control the concentrations of
these subtances.

Importance of metals

Metals of importance in the treatment, reuse, and disposal of treated effluents and biosolids are
summarized in table 2- 13, all living organisms require varying amounts (macro snd micro) of
metsllic slements; such as iron, chromium, copper, zinc, and cobalt, for proper growth. Although
macro and micro amounts of metals are required for proper growth, the same metals can be toxic
when present in elevated concentrations. As more use is made of treated wastewater effluent for
irrigation and landscape watering, a variety of metals must be determined to assess any adverse
effect that mayoccur. Calcium, magnesium, and sodium are of importance in determining the
sodium adsorption ratio (SAR), wich is used to assess the suitability of treated effluent for
agricultural use (sec Chap, 13). Where composted sludge is applied in agricultural applications,
arsenic, cadmium. Copper, lead, mercury, molybdenum, nickel, selenium, and zinc must be
determined.

Sources of Metals

The sourse of trace metals in wastewater include the discharges from residential dwellings,
groundwater infiltration, and commercial and industrial discharges. Many of the sources of
heavy metals are identified in Table 2-14, for examole, cadmium, chromates, lead, and mercury
are often present in induetrial wastes. These are found particularly in metal- plating wastes aand
should be removed by pretreatment at the site of the industry rather than be mixed with the
municipal wastewater. Fluoride, a toxic anion, is found commonly in wastewater from
alectronics from electronics manufacturing facilities.
Sampling and Methods of Analysis

Methods for determining the concentrations of these subtances vary in complexity according to
the interfering substance that may be present ( standard Methods, 1998). Metals are determined
typically by flame atomic absorption, electrothermal atomic absorption, inductively coupled
plasma, or IPC/mass spectrometry. Various classes of metals determined on an unfiltered sample
after digestion, and (4) acid extractable metals are those metals in solution after an unfiltered
sample is treated with a hot dilute mineral acid (Standard Methods, 1998)

Typical Effluent Discharge Limit For Metals

Increasingly, metallic constituents in effluent discharges and in biosolids are being regulated.
Typical discharge requirements for metals and other toxic constituents are reported in Table 2-
15.In addition to complying with existing U.S EPA requirements, many states have adopted
more restrictive standards to protect specific beneficial uses.

Table 2-14

Typical waste compunds produced by commercial, industrial, and agricultural activies that have
been classified as priority pollutants

Name formula use Cancern

Arsenic As

Barium Ba

Cadmium Cd

Chromium Cr

Lead Pb

Mercury Hg
Selenium Se

Silver Ag

2-6 AGGREATE ORGANIC CONSTUENTS

Organic compounds are normally composed of a combination of carbon, hydrogen, and oxygen,
together with nitrogen in some cases. The organic matter wastewater typically consistesof
proteins (40 to 12 percent), carbohydrates (25 to 50 percdent), and oils and fats (8 to 12 percent).
Urea, the major constituent of urine, is another important organic compound contributing to fresh
wastewater. Because urea decomposes rapidly, it is seldom found in orher than very fresh
wastewater. Along with the proteins, carbohydrates, fats and oils, and urea, wastewater
typidcally contains small quantities of a very large to extremely complet.

Over the years, a number of different analyses hyave been developed to determine the organic
content of wastewaters, In general, the analyses may be classified into those used to measure
aggregate organic matter comprising a number of organic constituents with similar
characteristics that cannot be distinguished separately. And those analyses used to quantify
individual organic compound (standard Method, 1998). Aggregate organic compounds are
constdered in this section. Individual organic compounds are considered in the following section.

Measurement of organic Content

In general, the analyses used to measure aggregate organic material may be divided in to those
used to measure gross concentrations of organic matter greate than about 1.0 mg?L and those
used to measure trace consentrations in the range of 10 -12 to 10 mg/L. Laboratory methods
commonly used today to measure gross amounts of organic matter (typically greater that) mg/L.
in wastewater include: (1) biochemical oxygen demand (BOD), (2) chemical oxygen demand
(COD) , and (3) total organic carbon (TOC), complementing these laboratory tests is the
theoretical oxygen demand (ThOD). Which is determined from the chemical formula of the
organic matter.
Other methods used in the past included: (1) total, albuminoid, organic, and ammonia nitrogen,
and (2) oxygen consumed, these determinations, with the exception of albuminoid nitrogen and
oxygen consumed, are still included in complete wastewater analyses. Their significance.
However, has changed. Where as formerly they were used almost exclusively to indicate organic
malter, they are now used to determine the availability of nitrogen to sustain biological activity
in industrial waste- treatment processes and to determine whether undestrable algal growths will
occur in receiving waters.

Trace organics in the range of 1012 to 10-13 mg/L are determined using instrumental methods
including gas chromatography and mass spectroscopy. Within the past 10 years, the sensitivity of
the methods used for the detection of trace organic compounds has improved significantly, and
detection of concentrations in the range of 10-9 mg/L is now almost a routine matter.

Biochemical Oxygen Demand (BOD)

The most widely used parameter of organic pollution applied to both wastewater and surface
water is the 5-day BOD (BOD5). This determination involves the measurement of the dissolved
oxygen used by microorganisms in the biochemical oxidation of organic matter. Despite the
widespread use of the BOD test, it has a number of limitation, as discussed later in this section. It
is hoped that, through the continued efforts of workers in the field, one of the other measures of
organic content, or perhaps a new measure, will ultimately he used in its place. Why, then if the
test suffers from serious limitations, is further spasce devoted to it in this text? The reason is that
BOD test results are now used (1) to determine the approximare quantity of oxygen that will be
required to biologically stabilize the organic matter present. (2) to determine the size of waste-
treatment facilities, (3) to measure the efficiency of some treatment processes, and (4) to
determine compliance with wastewater discharge permits. Because it is likely that the BOD test
will continue to be used for some time, it is important to know the details of the test and its
limitations

Basis For BOD Test. If sulficient oxygen is available, the aerobic biological decomposition of an
organic waste will continue until all of the wastebis consumed. Three more ore less distinct
activies occur. First, a portion of the waste is oxidized to end products to obtain energy for cell
maintenance and the synthesis of new cell tissue.

Simultaneously, some of the waste converted in to new cell tissue using part of the energy
released during oxidation. Finally, when the organic matter is used up, the new cells begin to
consume their own cell tissue to obtain energy for cell maintenance. This third process is called
endogenous respiration. Using the term COHNS (Wich represent the element carbon, oxygen,
hydrogen, nitrogen, and sulfur) to represent the organic wasteband the term C 5H7NO2 first
proposed by hoover and porges (1952) to represent cell tissue, the three processes are defined by
the following generalized chemical reactions:

Oxidation:

COHNS + O2 – bactena CO2 + H2O + NH3+ other endproducts + energy

(2-53)

Synthesis :

COHNS + O2 + bacteria – energy C5H7NO2

New cell tissue

(2-54)

Endogenous respiration :

C5H7NO2 + SO2 5CO2 + 2H20

(2-55)

If only the oxidation of the organic carbon that is present in the waste is considered, the ultimate
BOD is the oxygen required to complete the three reactions given above. This oxygen demand is
known as the ultimate carbonaceous of first- stage BOD, and is usually denoted as UBOD.

BOD Test Procedure. In the standard BOD test (see Fig. 2-19a), a small sample of the
wastewater to be tested is placed in a BOD bottle (volume = 300 mL). The bottle is then filled
with dilution water saturated in oxygen and containing the nutrients required for biological
growth. To ensure that meaningful results are obtained, the sample must be suitably diluted with
a specially prepared dilution water so that adequate nutrient and oxygen will be available during
the incubation period. Normally, several dilutions are prepared to cover the complete range of
possible values. The ranges of BOD that can be measured with various diluttions based on
percentage mixtures and direct pipetting are reported in table 2-16. Before the bottle is stoppered,
the oxygen concentration in the bottle is measured (see Fig 2-20).

After the bottle is incubated for 5 days at 20 ˚c, the dissolved oxygen concentration is measured
again. The BOD of the sample is the difference in the dissolved oxygen concentration is
measured again. The BOD of the sample is the difference in the dissolved oxygen concentration
values, expressed in milligrams per liter, divided by the decimal fractionbof sample used. The
computed BOD value is known as the 5-day, 20˚C biochemical oxygen demand. When testing
waters with low concentrations of microorganisms, a seeded BOD test is conducted (see Fig. 2-
19b). The organisms contained in the effluent from primary sedimentation facilities are used
commonly as the seed for the BOD test. Seed organisms can also be obtained commercially.
When the sample contains a large population of microorganisms (e.g., untreated wastewater),
seeding is not necessary.

The standard incubation period is usually 5 day at 20˚C, but other lengths of time and
temperatures can be used. Longer time periods (typically 7 days), which correspond to work
schedules, are often used, especially in small plants where the laboratory

Staff is not available on the weekends. The temperature, however, should be constant througbout
the test. The 20 ˚C temperature used is an average value for slow-moving streams in temperate
climates and is easily duplicated in an incubator. Different results would be obtained at different
tempetratures, because biochemical reaction rates are Table 2-16 Measurable BOD using various
dilutions of samples

Temperature- dependent. After incubation. The dissolved oxygen of the sample is measured (see
Fig. 2-20) and the BOD is calculated using Eq. (2-56) or (2- %&).

When the dilution water is not seeded:

 D1−d 2
BOD, mg/L=
P
(2-56)

When the difution water is seeded:

¿
BOD, mg/L= ( d 1−d 2 )−B 1−B 2¿ f P

(2-57)

Where D1= dissolved oxygen of diluted sampleimmediately after preparation, mg/L

D2= dissolved oxygen of diluted sample after 5-day incubation at 20˚C, mg/L
B1= dissolved oxygen of seed control before incubation,mg/L
B2= dissolved oxygen of seed control after incubation, mg/L
f = fraction of seeded dilution water volume in sample to volume of seeded dilution
water in seed control
P= fraction of wastewater sample volume to total combined volume
Biocemical oxidation theoretically takes an infinite time to go to completion because the rate
of oxidation is assumed to be proportional to the amount of organic matter remaining. Withing a
20-day period, the oxidation of the carbonaceous organic matter is about 95 to 99 percent
complete, and in the 5-day period used for the BOD test, oxidation is from 60 to 70 percent
complete.
Example 2-8 Determination of BOD from laboratory Data
The following information is available for a seeded 5-day BOD test conducted on a wastewater
sample.Fifteen mL of the waste sample was added directly in to a 300-mL BOD incubation
bottle. The initial DO of the diluted sample was 8.8 mg/L and the final DO after 5 days was 1.9
mg/L. The corresponding iitial and final DO of the seeded dilution water was 9.1 and 7.9,
respectively. What is the 5-day BOD (BOD5) of the wastewater sample?
1. Determine the 5-day BOD using Eq. (2-57).
( D1−D2 ) −( B 1−B 2 ) f
BOD, mg/L -
P
f = [(300 – 15)/300]= 0,95
P = 15/300 = 0,05
 ( 8.8−1.9 )−( 9.1−7.9 ) 0.95
BOD5,mg/L = =115.2 mg/ L
0.05

Modeling of BOD Reaction.

The rate of BOD oxidation (“exertion”) is modeled based on the assumption that the amount of
organic material remaining at any time is govemed by a first- order function ( see Chap. 4), as
given below.
dBODt
−k 1BODr (2-58)
dt
Integrating between the limits of (BOD and BODt and t = 0 and t = t yields
BODr = UBOD( e )
(2- 59)
Where BODr – amount of waste remaining at time t (days) expressed in oxygen equivalents.
Mg/L
K1 – first- order reaction rate constant
UBOD = Total or ultimate carbonaceous BOD, mg/L
L – time,d
Thus the BOD exerted up to time t is given by
BOD1= UBOD – BOD1 – UBOD – UBOD (e ) = UBOD (1- e ) (2.60)
Equation (2-60) is the standard expression used to define the BOD for wastewater. The
basis for this equation is discussed in sec, 4-3 in conjuction with the analysis of a batch reactor. It
should be noted that in the literature dealing with the characterization of wastewater the terms
“L” and “BOD” are often used to denote ultimate carbonaceous BOD (UBOD).
The value of k1 for untreated wastewater is generally about 0,12 to 0,46 d-1 (base e), with
a typical value of about 0,23 d-1,. The range of k1 values for effluents from biological treatment
process is from 0,12 to 0,23 d-1. For a given wastewater, the value of k1 at 20˚C can be
determined experimentally by observing the variation with time of the dissolved oxygen in a
series of incubated samples. If k1 at 20˚C is equal to 0,23 d-1, the 5-day oxygen demand is about
68 percent of the ultimate first- stage demand. Oceasionally, the first- order reaction rate constant
will be expresses in log (base 10) units. The relationship between k 1 (base e) and k1 (base 10) is
as follows :
K1 = k1 ɵT-