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Industrial Waste Program

Molybdenum Study
2007-2010

Department of Natural Resources and Parks

Wastewater Treatment Division

Table of Contents

1.0

Background ..............................................................................................................1

2.0

Introduction ..............................................................................................................1

3.0

The fate of molybdenum..........................................................................................2


3.1
3.2

4.0

Influent data
Biosolids data

Industrial user cooling tower survey ......................................................................2


4.1
4.2

Cooling tower data


Oil/Water separator data

5.0

Industrial user data..................................................................................................3

6.0

Recommendation......................................................................................................3

7.0

Implementation ........................................................................................................4

Prepared by Jim Sifford


December 5, 2011

1.0

Background
Concentrations of regulated metals in King County biosolids are consistently below the
most stringent state and federal standards for land application. However, certain
standards for molybdenum are under reconsideration by the U.S. Environmental
Protection Agency (EPA).
Following EPAs promulgation of Code of Federal Regulations (CFR), Title 40, Part 503,
Standards for the Use or Disposal of Sewage Sludge, the EPA was petitioned by
numerous groups to reconsider the molybdenum limits for biosolids to be land applied, in
light of concerns as to the technical basis utilized to develop the limits. In 1994, EPA
suspended all molybdenum concentration limits, with the exception of the ceiling limit
for land application pending further review. The current ceiling limit established for
molybdenum in land application is 75 milligrams per kilogram (mg/kg) (40 CFR 503.13).
A modified risk assessment to establish new molybdenum standards for land application
of biosolids was proposed in 2001. In 2006, EPA notified publicly owned treatment
works (POTWs) of its intent to assess the need and appropriate level for a numerical
standard for molybdenum in biosolids and suggested a pollutant concentration of 40
mg/kg; however, there has been no announcement to date.
New molybdenum limits for biosolids may be re-established by EPA. Depending on the
final pollutant concentrations, molybdenum could become the most limiting factor for
King County meeting all exceptional quality biosolids standards. With this in mind, the
King County Industrial Waste Program (KCIW) has looked at identifying sources and
corrective measures necessary to reduce the quantity of molybdenum being discharged
into the collection system.

2.0

Introduction
Typical commercial and industrial sources of waste molybdenum include pigments,
lubricants, catalysts, fertilizer, and corrosion control chemicals. According to EPA, the
amount of molybdenum in wastewater has increased since 1990 as commercial and
industrial operations began to replace chromium with less toxic molybdenum, used as a
corrosion inhibitor in cooling waters.
Studies throughout the U.S. have identified the use of molybdate-based corrosion control
chemicals in building heating and cooling systems as a potentially significant source of
molybdenum loadings to wastewater treatment plants. The water contained and circulated
in these heating and cooling systems typically contains residual corrosion control
chemicals, which is periodically discharged to the municipal sanitary sewer during
routine system purging events, blow downs or draining of the system, in preparation
for scheduled inspection and maintenance activities.

KCIW Molybdenum Study


December 5, 2011
Page 2

Based on the results of a major industrial user survey in 2006 and sampling data collected
in 2007, KCIW has identified the use of molybdate-based corrosion control chemicals in
industrial cooling towers as a significant source of molybdenum discharged to King
County wastewater treatment plants. These same molybdate-based corrosion chemicals
are also widely used in commercial building heating and cooling systems throughout the
County.
3.0

The fate of molybdenum


Once molybdenum reaches the treatment plant, about 80 to 90 percent of the
molybdenum detected in the influent passes through the treatment process and is
discharged in the effluent. It is expected that less than 10 percent is removed and
contained in the biosolids.
3.1

Influent data
In 2007, the analytical method detection limit for molybdenum was lowered to
0.026 micrograms per liter (g/L), allowing for more detectable results of the
daily influent concentration of molybdenum. Data from 2007 to 2010, indicates
that the average daily influent concentration of molybdenum at West Point
Treatment Plant (WPTP) is 7.0 g/L (5.0 pounds per day) and at South Treatment
Plant (STP) is 6.0 g/L (4.0 pounds per day).

3.2

Biosolids data
Data from 2007 to 2010 shows that the average concentration of molybdenum in
biosolids from both WPTP and STP is 10 mg/kg (dry weight basis). These levels
are well below the current regulatory ceiling limit of 75 mg/kg established for
molybdenum used for land application.

4.0

Industrial user cooling tower survey


Sodium molybdate is used as a corrosion inhibitor in solutions of antifreeze, paints, and
finishes and in the treatment of water for industrial cooling towers. The most likely
source of molybdenum in wastewater systems has been determined to be from cooling
towers used to supplement standard air conditioning and refrigeration systems and not
from other industrial contributors.
In 2006, KCIW conducted a limited survey of permitted industrial facilities with cooling
towers. KCIW sent the survey to 128 significant industrial users, which included
questions about product use, cooling tower size, chemical suppliers, pollution prevention
practices, and maintenance programs.

KCIW Molybdenum Study


December 5, 2011
Page 3

Thirty-three facilities completed and returned the survey (26 percent). Survey data
showed that 22 of these facilities operated cooling towers (67 percent of respondents) and
eight of those with cooling towers used corrosion control chemicals containing
molybdenum (36 percent of respondents).
4.1

Cooling tower data


In 2007, KCIW selected six of the largest industrial cooling tower systems using
molybdate-based corrosion control chemicals from the survey and collected grab
samples from their discharge sumps. Results show that the concentration of total
molybdenum in these samples ranged from 38 to 19,400 g/L.

4.3

Oil/Water separator data


Molybdenum disulfide is used in many industrial grade lubricants to significantly
reduce wear, friction, and sustain lubrication of machine components.
In August 2006, KCIW collected grab samples from 11 randomly chosen facilities
with industrial oil/water separators to see if there was a relationship between
molybdenum and used motor oil or petroleum products. The types of facilities
sampled included solid waste transfer stations, vehicle washing operations, pressure
washing operations, and metal recyclers. Results show that the concentration of
total molybdenum in these samples ranged from less than 20 to 2,310 g/L.

5.0

Industrial user data


KCIW also reviewed process wastewater data of industrial users to determine the
contribution of molybdenum discharged to King County sewers by permitted industries.
It is estimated that industrial users have the potential to discharge up to two pounds per
day of molybdenum to each treatment plant.

6.0

Recommendation
At this time, KCIW has determined that levels of molybdenum would be better controlled
through source management strategies and best management practices (BMPs) rather
than by developing numeric pretreatment limits.
This nonregulatory strategy would seek the voluntary cooperation of industry
representatives, building managers, and product manufacturers to develop BMP programs
on their own to reduce the discharge of molybdenum, including replacement of their
molybdate-based corrosion control chemicals with molybdate-free alternatives.

KCIW Molybdenum Study


December 5, 2011
Page 4

Should the pollutant concentration limits for molybdenum in biosolids be revised and
become more stringent, KCIW may re-evaluate this voluntary approach and seek other
measures to control the levels of molybdenum in our system.
7.0

Implementation
KCIW will make this recommendation available to the public through electronic media
sources and publications such as the KCIW Web pages and the KCIW Pretreatment
Newsletter.

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