Wastewater quality indicators

Wastewater quality indicators such as the biochemical oxygen demand (BOD) and the chemical oxygen
demand (COD) are essentially laboratory tests to determine whether or not a specific wastewater will have
a significant adverse effect upon fish or upon aquatic plant life.

Any oxidizable material present in a natural waterway or in an industrial wastewater will be oxidized both
by biochemical (bacterial) or chemical processes. The result is that the oxygen content of the water will be
decreased. Basically, the reaction for biochemical oxidation may be written as:
Oxidizable material + bacteria + nutrient + O2 → CO2 + H2O + oxidized inorganics such as NO3 or SO4
Oxygen consumption by reducing chemicals such as sulfides and nitrites is typified as follows:
S-- + 2 O2 → SO4--
NO2- + ½ O2 → NO3-
Since all natural waterways contain bacteria and nutrient, almost any waste compounds introduced into
such waterways will initiate biochemical reactions (such as shown above). Those biochemical reactions
create what is measured in the laboratory as the Biochemical Oxygen Demand (BOD).
Oxidizable chemicals (such as reducing chemicals) introduced into a natural water will similarly initiate
chemical reactions (such as shown above). Those chemical reactions create what is measured in the
laboratory as the Chemical Oxygen Demand (COD).
Both the BOD and COD tests are a measure of the relative oxygen-depletion effect of a waste contaminant.
Both have been widely adopted as a measure of pollution effect. The BOD test measures the oxygen
demand of biodegradable pollutants whereas the COD test measures the oxygen demand of biogradable
pollutants plus the oxygen demand of non-biodegradable oxidizable pollutants.
The so-called 5-day BOD measures the amount of oxygen consumed by biochemical oxidation of waste
contaminants in a 5-day period. The total amount of oxygen consumed when the biochemical reaction is
allowed to proceed to completion is called the Ultimate BOD. The Ultimate BOD is too time consuming, so
the 5-day BOD has almost universally been adopted as a measure of relative pollution effect.
There are also many different COD tests. Perhaps, the most common is the 4-hour COD.
It should be emphasized that there is no generalized correlation between the 5-day BOD and the Ultimate
BOD. Likewise, there is no generalized correlation between BOD and COD. It is possible to develop such
correlations for a specific waste contaminant in a specific wastewater stream, but such correlations cannot
be generalized for use with any other waste contaminants or wastewater streams.
The laboratory test procedures for the determining the above oxygen demands are detailed in the following
sections of the "Standard Methods For the Examination Of Water and Wastewater" available at
www.standardmethods.org:
5-day BOD and Ultimate BOD: Sections 5210B and 5210C
COD: Section 5220

Biochemical oxygen demand

Biochemical Oxygen Demand or Biological Oxygen Demand (BOD) is a chemical procedure for
determining how fast biological organisms use up oxygen in a body of water. It is used in water quality
management and assessment, ecology and environmental science. BOD is not an accurate quantitative test,
although it could be considered as an indication of the quality of a water source.
BOD can be used as a gauge of the effectiveness of wastewater treatment plants. It is listed as a
conventional pollutant in the U.S. Clean Water Act.

Most pristine rivers will have a 5-day BOD below 1 mg/L. Moderately polluted rivers may have a BOD
value in the range of 2 to 8 mg/L. Municipal sewage that is efficiently treated by a three-stage process
would have a value of about 20 mg/L or less. Untreated sewage varies, but averages around 600 mg/L in
Europe and as low as 200 mg/L in the U.S., or where there is severe groundwater or surface water
infiltration. (The generally lower values in the U.S. derive from the much greater water use per capita than
other parts of the world.)

The BOD5 test

BOD measures the rate of oxygen uptake by micro-organisms in a sample of water at a temperature of
20°C and over an elapsed period of five days in the dark.
There are two recognized methods for the measurement of BOD.

Dilution method
To ensure that all other conditions are equal, a very small amount of micro-organism seed is added to each
sample being tested. This seed is typically generated by diluting activated sludge with de-ionized water.
The BOD test is carried out by diluting the sample with oxygen saturated de-ionized water, inoculating it
with a fixed aliquot of seed, measuring the dissolved oxygen (DO) and then sealing the sample to prevent
further oxygen dissolving in. The sample is kept at 20 °C in the dark to prevent photosynthesis (and thereby
the addition of oxygen) for five days, and the dissolved oxygen is measured again. The difference between
the final DO and initial DO is the BOD. The apparent BOD for the control is subtracted from the control
result to provide the corrected value.
The loss of dissolved oxygen in the sample, once corrections have been made for the degree of dilution, is
called the BOD5. For measurement of carbonaceous BOD (cBOD), a nitrification inhibitor is added after
the dilution water has been added to the sample. The inhibitor hinders the oxidation of nitrogen.
BOD can be calculated by:
Undiluted: Initial DO - Final DO = BOD
Diluted: ((Initial DO - Final DO)- BOD of Seed) x Dilution Factor
BOD is similar in function to chemical oxygen demand (COD), in that both measure the amount of organic
compounds in water. However, COD is less specific, since it measures everything that can be chemically
oxidised, rather than just levels of biologically active organic matter.

Manometric method
This method is limited to the measurement of the oxygen consumption due only to carbonaceous oxidation.
Ammonia oxidation is inhibited.
The sample is kept in a sealed container fitted with a pressure sensor. A substance that absorbs carbon
dioxide (typically lithium hydroxide) is added in the container above the sample level. The sample is stored
in conditions identical to the dilution method. Oxygen is consumed and, as ammonia oxidation is inhibited,
carbon dioxide is released. The total amount of gas, and thus the pressure, decreases because carbon
dioxide is absorbed. From the drop of pressure, the sensor electronics computes and displays the consumed
quantity of oxygen.
The main advantages of this method compared to the dilution method are:
simplicity: no dilution of sample required, no seeding, no blank sample
direct reading of BOD value
continuous display of BOD value at the current incubation time.
Furthermore, as the BOD measurement can be monitored continuously, a graph of its evolution can be
plotted. Interpolation of several graphs on a similar water may build an experience of its usual evolution,
and allow an estimation of the five days BOD after as early as the first two days of incubation.[1]

History of the use of BOD

The Royal Commission on River Pollution, which was established in 1865 and the formation of the Royal
Commission on Sewage Disposal in 1898 led to the selection in 1908 of BOD5 as the definitive test for
organic pollution of rivers. Five days was chosen as an appropriate test period because this is supposedly
the longest time that river water takes to travel from source to estuary in the U.K. In 1912, the commission
also set a standard of 20 ppm BOD5 as the maximum concentration permitted in sewage works discharging
to rivers, provided that there was at least an 8:1 dilution available at dry weather flow. This was contained
in the famous 20:30 (BOD:Suspended Solids) + full nitrification standard which was used as a yardstick in
the U.K. up to the 1970s for sewage works effluent quality.

References

Clair N. Sawyer, Perry L. McCarty, Gene F. Parkin (2003). Chemistry for Environmental Engineering and
Science (5th edition ed.). New York: McGraw-Hill. ISBN 0-07-248066-1.
Lenore S. Clescerl, Arnold E. Greenberg, Andrew D. Eaton. Standard Methods for Examination of Water
& Wastewater (20th edition ed.). Washington, DC: American Public Health Association. ISBN 0-87553-
235-7.

Chemical oxygen demand

In environmental chemistry, the chemical oxygen demand (COD) test is commonly used to indirectly
measure the amount of organic compounds in water. Most applications of COD determine the amount of
organic pollutants found in surface water (e.g. lakes and rivers), making COD a useful measure of water
quality. It is expressed in milligrams per liter (mg/L), which indicates the mass of oxygen consumed per
liter of solution. Older references may express the units as parts per million (ppm).

The basis for the COD test is that nearly all organic compounds can be fully oxidized to carbon dioxide
with a strong oxidizing agent under acidic conditions. The amount of oxygen required to oxidize an organic
compound to carbon dioxide, ammonia, and water is given by:

This expression does not include the oxygen demand caused by the oxidation of ammonia into nitrate. The
process of ammonia being converted into nitrate is referred to as nitrification. The following is the correct
equation for the oxidation of ammonia into nitrate.

The second equation should be applied after the first one to include oxidation due to nitrification if the
oxygen demand from nitrification must be known. Dichromate does not oxidize ammonia into nitrate, so
this nitrification can be safely ignored in the standard chemical oxygen demand test.
The International Organization for Standardization describes a standard method for measuring chemical
oxygen demand in ISO 6060 [1].

History

For many years, the strong oxidizing agent potassium permanganate (KMnO4) was used for measuring
chemical oxygen demand. Measurements were called oxygen consumed from permanganate, rather than
the oxygen demand of organic substances. Potassium permanaganate's effectiveness at oxidizing organic
compounds varied widely, and in many cases biochemical oxygen demand (BOD) measurements were
often much greater than results from COD measurements. This indicated that potassium permanganate was
not able to effectively oxidize all organic compounds in water, rendering it a relatively poor oxidizing agent
for determining COD.
Since then, other oxidizing agents such as ceric sulfate, potassium iodate, and potassium dichromate have
been used to determine COD. Of these, potassium dichromate (K2Cr2O7) has been shown to be the most
effective: it is relatively cheap, easy to purify, and is able to nearly completely oxidize almost all organic
compounds.
In these methods, a fixed volume with a known excess amount of the oxidant is added to a sample of the
solution being analyzed. After a refluxing digestion step, the initial concentration of organic substances in
the sample is calculated from a titrimetric or spectrophotometric determination of the oxidant still
remaining in the sample.

Using potassium dichromate

Potassium dichromate is a strong oxidizing agent under acidic conditions. (Acidity is usually achieved by
the addition of sulfuric acid.) The reaction of potassium dichromate with organic compounds is given by:

where d = 2n/3 + a/6 - b/3 - c/2. Most commonly, a 0.25 N solution of potassium dichromate is used for
COD determination, although for samples with COD below 50 mg/L, a lower concentration of potassium
dichromate is preferred.
In the process of oxidizing the organic substances found in the water sample, potassium dichromate is
reduced (since in all redox reactions, one reagent is oxidized and the other is reduced), forming Cr3+. The
amount of Cr3+ is determined after oxidization is complete, and is used as an indirect measure of the
organic contents of the water sample.

Blanks
Because COD measures the oxygen demand of organic compounds in a sample of water, it is important that
no outside organic material be accidentally added to the sample to be measured. To control for this, a so-
called blank sample is required in the determination of COD (and BOD, for that matter). A blank sample is
created by adding all reagents (e.g. acid and oxidizing agent) to a volume of distilled water. COD is
measured for both the water and blank samples, and the two are compared. The oxygen demand in the
blank sample is subtracted from the COD for the original sample to ensure a true measurement of organic
matter.

Measurement of excess
For all organic matter to be completely oxidized, an excess amount of potassium dichromate (or any
oxidizing agent) must be present. Once oxidation is complete, the amount of excess potassium dichromate
must be measured to ensure that the amount of Cr3+ can be determined with accuracy. To do so, the excess
potassium dichromate is titrated with ferrous ammonium sulfate (FAS) until all of the excess oxidizing
agent has been reduced to Cr3+. Typically, the oxidation-reduction indicator Ferroin is added during this
titration step as well. Once all the excess dichromate has been reduced, the Ferroin indicator changes from
blue-green to reddish-brown. The amount of ferrous ammonium sulfate added is equivalent to the amount
of excess potassium dichromate added to the original sample.

Preparation Ferroin Indicator reagent

A solution of 1.485 g 1,10-phenanthroline monohydrate is added to a solution of 695 mg FeSO4·7H2O in

water, and the resulting red solution is diluted to 100 mL.
[edit]Calculations
The following formula is used to calculate COD:

where b is the volume of FAS used in the blank sample, s is the volume of FAS in the original sample, and
n is the normality of FAS. If milliliters are used consistently for volume measurements, the result of the
COD calculation is given in mg/L.
The COD can also be estimated from the concentration of oxidizable compound in the sample, based on its
stoichiometric reaction with oxygen to yield CO2 (assume all C goes to CO2), H2O (assume all H goes to
H2O), and NH3 (assume all N goes to NH3), using the following formula:
COD = (C/FW)(RMO)(32)
Where C = Concentration of oxidizable compound in the sample,
FW = Formula weight of the oxidizable compound in the sample,
RMO = Ratio of the # of moles of oxygen to # of moles of oxidizable compound in their reaction to CO2,
water, and ammonia
For example, if a sample has 500 wppm of phenol:
C6H5OH + 7O2 → 6CO2 + 3H2O
COD = (500/94)(7)(32) = 1191 wppm

Inorganic interference

Some samples of water contain high levels of oxidizable inorganic materials which may interfere with the
determination of COD. Because of its high concentration in most wastewater, chloride is often the most
serious source of interference. Its reaction with potassium dichromate follows the equation:

Prior to the addition of other reagents, mercuric sulfate can be added to the sample to eliminate chloride
interference.
The following table lists a number of other inorganic substances that may cause interference. The table also
lists chemicals that may be used to eliminate such interference, and the compounds formed when the
inorganic molecule is eliminated.
Inorganic molecule Eliminated by Elimination forms
Chloride Mercuric sulfate Mercuric chloride complex
Nitrite Sulfamic acid N2 gas
Ferrous iron - -
Sulfides - -

Government regulation

Many governments impose strict regulations regarding the maximum chemical oxygen demand allowed in
wastewater before they can be returned to the environment. For example, in Switzerland, a maximum
oxygen demand between 200 and 1000 mg/L must be reached before wastewater or industrial water can be
returned to the environment [2].

Indikator Kualitas Limbah

Indikator Kualitas Limbah seperti kebutuhan oksigen biokimia ( BOD) dan kebutuhan oksigen kimia
( COD) merupakan pengujian laboratorium yang sangat penting untuk menentukan ya atau tidaknya suatu
limbah tertentu akan mempunyai suatu efek yang kurang baik terhadap ikan atau kehidupan tanaman air.
Beberapa zat yang dapat dioksidasi pada aliran air atau suatu limbah industri akan dioksidasi baik melalui
biokimia atau proses kimia. Hasilnya adalah kandungan oksigen dari air akan berkurang. Pada dasarnya,
reaksi untuk oksidasi biokimia bisa ditulis sebagai ini:
zat yang dapat dioksidasi + bakteri+ nutrient + O2 --> CO2+ H2O+ inorganik yang teroksidasi seperti NO3
atau So4 konsumsi oksigen dengan mengurangi bahan-kimia seperti sulfida dan nitrites khususnya sebagai
berikut:

S-- + 2 O2 --> SO4--

S--+ 2 O2 --> SO4--

NO2- + ½ O2 --> NO3-

NO2-+½ O2 --> NO3-

Karena semua aliran air alami mengandung bakteri dan nutrient, hampir setiap senyawa limbah yang
masuk ke dalam aliran akan memulai reaksi biokimia ( seperti ditunjukkan di atas). Reaksi biokimia
tersebut menciptakan apa yang terukur di laboratorium sebagai kebutuhan Oksigen biokimia ( BOD).
Zat Kimia yang dapat dioksidasi ( seperti zat pereduksi) yang masuk ke dalam air akan serupa memulai
reaksi kimia ( seperti ditunjukkan di atas). Reaksi kimia itu seperti apa yang terukur di laboratorium
sebagai kebutuhan Oksigen kimia ( COD).
Kedua uji BOD dan COD adalah suatu ukuran dari oxygen-depletion efek yang relatif dari suatu
kontaminan limbah. Kedua-Duanya telah secara luas diadopsi sebagai ukuran dari efek polusi. Uji BOD
mengukur kebutuhan oksigen dari pengotor yang biodegradable sedangkan COD mengukur kebuthan
oksigen dari pengotor yang biogradable plus oksigen dari pengotor yang non-biodegradable.
Yang disebut BOD-5 hari mengukur jumlah oksigen yang dikonsumsi oleh oksidasi biokimia dari
kontaminan limbah dalam waktu 5 hari. Total jumlah oksigen yang dikonsumsi ketika reaksi biokimia
dibiarkan untuk menyelesaikan Bod seluruhnya. Bod keseluruhan terlalu menghabiskan waktu, sehingga
BOD 5 hari mempunyai hampir mewakili sebagai ukuran relatif dari efek polusi.
COD juga memiliki keragaman tapi yang paling umum adalah COD 4 jam.
Haruslah ditekankan bahwa tidak bisa disamaratakan korelasi antara BOD-5 hari dengan Bod lengkap
(ultimate). Demikian Juga, tidak ada korelasi antara BOD dan COD. korelasi seperti itu dapat untuk
dikembangkan untuk kontaminan limbah tertentu pada arus limbah tertentu, tetapi korelasi seperti itu
tidak bisa disamaratakan untuk digunakan pada limbah yang berbeda.

Kebutuhan oksigen biokimia

kebutuhan Oksigen biokimia atau kebutuhan Oksigen biologi ( BOD) adalah suatu prosedur kimia untuk
menentukan seberapa cepat organisma biologi menghabiskan oksigen dalam air. Digunakan dalam
penilaian dan manajemen kualitas air, ekologi dan ilmu lingkungan. BOD bukanlah suatu test yang
kwantitatif akurat, walaupun bisa dijadikan sebagai indikasi dari mutu sumber mata air.
BOD dapat digunakan sebagai sebagai suatu meteran dari efektivitas dari pabrik pengolahan limbah.
Sungai yang paling murni akan mempunyai BOD-5 hari di bawah 1 mg/L. Sungai yang tercemar sedang
dengan BOD sekitar 2 sampai 8 mg/L.

Uji BOD5

BOD mengukur tingkat pengambilan oksigen oleh micro-organisms di dalam contoh air pada suatu
temperatur dari 20°C pada 5 hari periode yang gelap.
Ada dua metoda yang umum untuk pengukuran dari BOD.

1. Metoda pengenceran

Untuk memastikan bahwa semua kondisi-kondisi sudah sama, sejumlah kecil jumlah benih jasad renik
ditambahkan ke masing-masing contoh diuji. Benih ini dihasilkan dengan mengencerkan activated sludge
dengan air yang de-ionized. Uji BOD dilaksanakan dengan mengencerkan sample dengan oxygen
saturated de-ionized water, menginokulasinya dengan suatu benih, mengukur oksigen terlarut (DO) dan
kemudian menyegel sample untuk mencegah oksigen masuk ke dalamnya. Sample didiamkan pada 20 ° C
di dalam gelap untuk mencegah fotosintesis ( penambahan dari oksigen lagi) selama lima hari, dan oksigen
yang terlarut diukur lagi. Perbedaan antara DO akhir dan awal adalah BOD itu. Bod nyata untuk blanko
ditentukan untuk koreksi.
Hilangnya oksigen terlarut dalam sample, koreksi harus dibuat untuk tingkat pengenceran, disebut BOD5.
Untuk pengukuran dari BOD yang mengandung zatarang ( cBOD), suatu penghambat nitrification
ditambahkan setelah air pengenceran dilakukan terhadap sample. Penghambat mencegah oksidasi dari
nitrogen.

BOD dapat dihitung :

Tidak diencerkan: DO awal - DO ahir = BOD

Diencerkan: ((DO awal - DO ahir)- BOD benih) x faktor pengenceran BOD serupa dengan kebutuhan
oksigen kimia (COD), oleh karena kedua-duanya ukuran jumlah campuran yang organik di dalam air. maka
COD kurang spesifik, karena terukur semua zat yang bisa dioksidasi secara kimia, dibanding tingkat
organik biologik yang aktif.

2. Metoda manometris

Metoda ini dibatasi untuk pengukuran konsumsi oksigen untuk oksidasi yang mengandung karbon.
Oksidasi amoniak dilarang.
Contoh disegel dalam wadah yang cocok yang memiliki sensor tekanan. Suatu unsur yang menyerap gas
C02 ( khususnya litium hidroksida) ditambahkan di atasnya ke dalam wadah. Sample disimpan seperti pada
metoda pengenceran. Konsumsi oksigen, seperti oksidasi amoniak dihambat, C02 dilepaskan. Total jumlah
gas, berkurang sebab gas C02 diserap. Dari penurunan tekanan, sensor elektronik menghitung dan
menampilkan jumlah oksigen yang dikonsumsi.
Keuntungan dari metoda ini dibandingkan dengan metoda pengenceran adalah:
Sederhana: tidak perlu pengenceran, tidak ada pembenihan, tidak perlu blanko dengan nilai display
continuous sehingga bisa dibuat grafik

Kebutuhan Oksigen kimia (COD)

Di dalam ilmu kimia lingkungan, uji kebutuhan oksigen kimia (COD) biasanya digunakan untuk secara
tidak langsung mengukur jumlah senyawa organik dalam air. Kebanyakan aplikasi COD menentukan
jumlah pengotor organik yang ditemukan pada air permukaan ( e.g. danau dan sungai), sehingga COD
bermanfaat untuk ukuran kualitas air. Dinyatakan dalam miligram per liter ( mg/L), yang menunjukkan
konsumsi massa oksigen per liter larutan atau ppm.
Dasar untuk uji COD adalah bahwa hampir semua senyawa organik dapat dioksidasi menjadi gas C02
dengan oksidator kuat pada kondisi asam. Jumlah oksigen yang diperlukan mengoksidasi senyawa organik
menjadi gas C02, amoniak, dan air adalah:
Tidak termasuk kebutuhan oksigen untuk mengoksidasi dari amoniak ke dalam nitrat. Proses dari amoniak
diubah jadi nitrat adalah dikenal sebagai nitrification.
Persamaan yang kedua harus digunakan setelah nomor satu meliputi oksidasi yang berkaitan dengan
nitrification jika kebutuhannya diketahui. Dichromate tidak mengoxidasi amoniak ke dalam nitrat, maka
nitrification ini dapat diabaikan pada uji COD baku.

Sejarah

Selama bertahun-tahun, oksidator kuat kalium permanganat ( KMNO4) telah digunakan untuk mengukur
COD. Pengukuran disebut konsumsi oksigen permanganate, daripada kebutuhan oksigen zat organik.
Efektivitas kalium permanaganate pada oksidasi senyawa organik sangat bervariasi, dan dalam beberapa
kasus BOD pengukuran sering jauh lebih besar dibanding hasil dari pengukuran COD. Permanganat kalium
menunjukkan bahwa ini tidak mampu secara efektif mengoxidasi semua senyawa organik di dalam air.
Karenanya, oksidator lain seperti ceric sulfate, kalium iodat, dan kalium dichromate telah digunakan untuk
menentukan COD. Dari semua ini, kalium dichromate ( K2Cr2O7) terbukti paling efektif: relatif murah,
murni, dan hampir bisa mengoksidasi sempurna hampir semua senyawa organik.
Didalam metoda ini, suatu volume tertentu oksidator berlebih ditambahkan ke larutan sample yang akan
dianalisa. Setelah langkah digest refluks, konsentrasi awal senyawa organik dalam sample dihitung melalui
penentuan yang spectrophotometric atau titrimetric dari oksidator yang tersisa di dalam sample.

Penggunaan kalium dikromat

kalium Dichromate adalah oksidator kuat pada kondisi asam. (Keasaman biasanya diperoleh dengan
penambahan asam sulfat). Reaksi dari kalium dichromate dengan senyawa organik adalah:

di mana d= 2n/3+ a/6- b/3- c/2. Umumnya 0.25 N larutan kalium dichromate digunakan untuk penentuan
COD , walaupun untuk COD di bawah 50 mg/L, penurunan konsentrasi kalium dichromate lebih baik.

Karena COD mengukur kebutuhan oksigen senyawa organik dalam contoh air, sangat penting agar tidak
ada zat organik dari luar yang secara tidak disengaja ditambahkan ke sample yang diukur. Untuk
mencegahnya, penentuan COD blanko diperlukan ( juga BOD).