PRETREATMENT CORNER

Biocides and Their Relationship to Pretreatment Programs

By Judy F. Musselman, QEP

Just what is a biocide? Websters Dictionary defines it as a substance that is destructive to many different organisms. In the water treatment field, a biocide is a substance that inhibits the growth of nuisance organisms such as algae, bacteria and fungi. Many industrial facilities that require very clean or pure water for their processes or for use in cooling towers or boilers use biocides in pretreating the water prior to use. A few examples of industrial processes in which biocides are used include, but are not limited to: aqueous parts cleaners, metalworking fluids, corrugated paper industry, tanneries, textile manufacturing and food processing. Biocides are also present in many household products such as adhesives, deodorant soap, mouthwash and paint, to name a few. Biocidal compounds may include both oxidizing and non-oxidizing biocides. Oxidizing biocides inhibit growth and are quick killing. Some of the more common oxidizing biocides are Bromine, Chlorine, Chlorine Dioxide and Ozone. Non-oxidizing biocides, however, cover a wider spectrum of chemical types, are generally stable, have longer lasting effects and are therefore slower killing. Examples of non-oxidizing biocidal compounds include carbamate, dodecylguanidine, glutaraldehyde, isothiazoline, methylenebis-thiocyanate, organo-bromide, organo-tin/quaternary ammonium salts, quaternary ammonium salts and triazine. Are biocides harmful to the biological system at a municipal wastewater treatment plant? Yes and no, depending on the type and concentration of the biocides chemical components. For example (this is a true story), a textile manufacturer uses bleach in one of its processes and discharges the rinse water from this particular operation to the sewer system. If the industry contributes a significant portion of the flow to the municipal wastewater treatment plant and a residual disinfectant level is still present in the influent to the municipal wastewater treatment plant, the disinfectant could have a deleterious effect on the bacteria in the activated sludge. So should you start testing your influent for residual disinfectant? Perhaps you already do if your laboratory tests the influent for BOD. Part of the set-up for the BOD test involves testing for chlorine and then dechlorinating the samples prior to dilution and analysis. Another example involves an industry that adds biocides to the potable water for use in a boiler. The boiler blowdown water is discharged to the sewer system, however, both the biocide chemical concentration and volume are insignificant compared to the total flow received at the municipal wastewater treatment plant, so that no harmful effects from the biocide will be observed due to dilution. This brings us back to the old adage, dilution is not the solution to pollution. So where do we draw the line? Are biocides harmful to the aquatic life in the receiving stream? Again, yes and no, depending on the type and concentration of the biocides chemical components. We are familiar with the effects of Chlorine and its relatives, however, the non-oxidizing biocides may have a few surprises. Many of these biocides, in their natural states, are either very acidic or very alkaline. The following table provides a few examples of the effects of products within each chemical family.

Biocide Chemical Family

Activated Sludge

COD mg/L

TOC mg/L

pH Standard

Fathead Minnow

Ceriodaphni a Dubia

LC50 mg/L Carbamates Glutaraldehyde Isothiazoline Methylene-Bis Thiocyanate Organo-Bromide Organo-Tin Triazine 34 20,000 7,850 425,000

Unit 10.5-12.4 3.1-4.5 3.0-5.0

LC50 mg/L

LC50 mg/L 11.5

8 0.6

15 0.06 1.24 1.0-10.0

1,110,000

280,000

2.0-5.0 10.5

1.36 5.0-500

A review of applicable Material Safety Data Sheets (MSDS) from contributing industrial facilities in your sewer service area should be made to determine if any biocides contain appreciable quantities of hazardous ingredients. Some proprietary biocides may not even list the hazardous ingredients. One recently prepared MSDS listed Sodium Dimethyldithiocarbamate as being present but yet stated that no ecological information is available. However, in a previous Pretreatment Corner article from the May/June 2002 issue of the Keystone Water Quality Manager, Sodium Dimethyldithiocarbamate is known to be toxic to aquatic life and can combine with, or break down, to form other toxic chemicals, including Thiram and Ziram, both EPA registered fungicides, as well as other dithiocarbamates, carbon disulfide and dimethylamine. Some of these compounds may cause biological inhibition at the POTW wastewater treatment plant, and ultimately pass through to the receiving stream, causing further toxicity to the aquatic life in the receiving stream. Perhaps chemical manufacturers should be required to provide ALL toxicological data on a biocide MSDS instead of pleading ignorance and stating UNKNOWN! North Carolina provides information at its URL, www.esb.enr.state.nc.us/ATUwww/Default.html#Biocide, to determine the allowable biocide concentration that may be discharged to the receiving stream to protect aquatic life. It is worth a look!