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H
Cl
Cl
C
Cl
C
Cl
Cl
Dichlorodiphenyltrichloroethane
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DDT

• DDT was banned for sale in the U.S. on January 1,
  1973
• In 1993, DDT was the third most frequently
  detected pesticide on produce entering the U.S.
• Prior to its being banned DDT was accumulating in
  the fat of humans and all other animals including
  Arctic seals, and Antarctic penguins even though
  these animals were far removed from any point of
  application. Further study showed that birds
  were acquiring high levels of DDT by
  biomagnification

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• DDT was classified as a suspected occupational
  carcinogen that should be handled cautiously in
  the workplace.
• Statistically significant correlation between
  high body burdens of DDT and breast cancer were
  observed. (Correlation does not establish cause
  and effect, There is a significant correlation
  between the number of Baptist ministers in a City
  and liquor consumption.)
• At a site in California people found DDT the size
  of bowling balls under houses surrounding the
  site that was abandoned by a chemical company
  still in business. EPA bought the homes. Sewers
  leading to the ocean so contaminated they are
  being cleaned by hand. Hazmat suits and buckets.

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• The California site is a superfund site and its
  history is all to reminiscent of other sites
  around the country.
• The Palos Verdes Shelf Superfund site is an area
  of contaminated sediment off the Palos Verde
  Peninsula. The contaminated sediment lies in the
  Pacific Ocean at depths of 50 ft. or more, too
  deep for human contact. However, the fish found
  in the Plaos Verdes Shelf area contain high
  concentrations of DDT and PCBs, concentrations
  that continue to pose a threat to human health
  and the natural environment.
• The U.S. Justice Department and the California
  Attorney General in 1990 filed suit under the
  federal Superfund Law, alleging that Montrose
  Chemical Corporation of California, Aventis
  CropScience USA, Inc., Chris-Craft Industries
  Inc. and Atkemix Thirty Seven Inc., either owned
  or operated a DDT manufacturing plant in Los
  Angeles County.

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• Montrose Chemical Corp. Was the nations largest
  manufacturer of DDT. From the 1950s to the 1971
  tons of DDT were dumped into the sewer system.
  In 1971, the last year Montrose used the county
  sewers, an estimated 50,500 lbs.
• The settlement (2000) brought the total amount
  for environmental restoration to 137.5 million.
  The US and California previously reached similar
  settlements with County Sanitation District No. 2
  of LA which operated the sewers that conveyed the
  DDT to the ocean about 150 municipalities that
  discharged other substances through the sewers
  and three other corporate defendants Potlach,
  Simpson, and CBS/Westinghouse that discharged
  PCBs through the sewers and into the ocean.
• Some of the DDT and PCB contaminated sediment has
  been capped. The question that remains is what
  to do with the rest of the contaminated sediment
  and will the sediment stay capped?
• What to do about the human health risks from
  contaminated fish.

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• Most of the DDT on Palos Verdes Shelf converted
  quickly to DDE or DDD, two DDT related compounds.
  Recent analysis suggests that reductive
  dechlorination continues for DDT but PCB
  concentrations are not breaking down.
• There are many ways in which capped DDT and PCBs
  may not stay in place biological, chemical, and
  physical processes are being investigated.
• The second area of concern is contaminated fish
  consumption so EPA and the State have undertaken
  an extensive outreach program. To warn people of
  the dangers of eating the contaminated fish. The
  outreach efforts have been conducted in English,
  Spanish, Cambodian, Chinese, Filipino, Korean,
  Vietnamese, Chamorro, Samoan, Marshallese, and
  Tongan. Who says we are not a country of
  emigrants.
• Handout ..

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Herbicides account for 69 of all pesticides used
by American farmers, insecticides 19 and
fungicides 12. Four crops corn, cotton, wheat,
and soybeans account for about 70 of the
insecticides and 80 of the herbicides used on
crops each year. Fungicides are used primarily
to treat seeds and to protect fruits and
vegetables during the growing season and after
harvest. About 20 of the pesticides used each
year in the U.S. are applied to lawns, gardens,
parks, golf courses, and cemeteries. The average
home owner applies about 5 times more pesticide
per unit of land area than do farmers. Each
year, Americans spend about 1.5 billion dollars
on pesticides used on lawns.
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Bioavailable term used to describe the
availability of chemicals or materials to living
organisms. Measurements of total concentrations
of chemicals in water or sediments does not
necessarily indicate that the chemical measured
is in a form that can be taken up by organisms
Bioaccumulation General term describing a
process by which chemicals are taken up by
aquatic organisms from the water directly, or
through consumption of food containing the
chemicals. Bioconcentration A process by which
there is a net accumulation of a chemical
directly from water into aquatic organisms (e.g.,
by gill, epithelial tissue, or through cell
walls) Biomagnification A process by which
there is a net accumulation of a chemical as the
chemical passes up through two or more trophic
levels. The term implies an efficient transfer
of a chemical from food to consumer, so that the
residue concentrations increase systematically
from one trophic level to the next.
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Biomagnification of a Persistent Pesticide DDT

PPM DDT Residue Water

0.00005 Plankton

0.04 Silverside Minnow
0.2
Sheepshead Minnow
0.9 Pickerel (Predatory Fish)

1.3 Needlefish (Predatory Fish)
2.1 Heron (Bird, feeds on
small animals) 3.6 Tern
(Bird, feeds on small animals)
3.9 Herring Gull (Scavenger)
6.0 Fish Hawk
(Osprey egg)
13.8 Merganser (Fish eating duck)
22.8 Cormorant (Feeds
on large fish)
26.4 BMF (Biological Magnification Factor)
26.4/0.00005 528,000 BMF ratio of
concentration in the organism divided by the
concentration in the medium.

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Characteristics of DDT Class of chemicals
Naturally occurring? - Synthetic or Manmade?
Bioaccumulate - Bioconcentrate - Biomagnify
- Hydrophilic - Hydrophobic - Lipophilic -
Lipophobic - If you go into the field to look
for DDT what should you be aware of?
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DDT refers to a technical grade which is usually
composed of 77.1 p,p-DDT 14.9
o,p-DDT 0.3
p,p- DDT 0.1 o,p -DDD 4.0
p,p -DDE 0.1
o,p DDE 3.5 unidentified
compounds Mirex to Kepone
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All things are connected Reported by Dr. Paul
Ehrlich In the early 1960s DDT was sprayed on
the thatched roofs and vegetation around villages
in Borneo to kill mosquitoes and control malaria.
The DDT killed the mosquitoes very successfully,
but poisoned all the insects which were eaten by
the gecko lizards that inhabited the houses. The
geckos accumulated so much DDT that they too
died. Moths, which previously had been kept
under control by the geckos, ate the palm thatch
and caused the roofs to collapse. Village cats
ate the geckos and were themselves poisoned
allowing rats to descend on the villages
unleashing an epidemic of bubonic plague. To
kill the rats the government parachuted cats into
some of the remote villages. Sometimes actions
that are not well thought out have complex and
unsuspected consequences.
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Eco-colonialism Malaria, an old scourge long
thought vanquished, has returned to South Africa.
In 1931-32 a malaria epidemic killed more than
22,000 people in the region. After health
authorities began spraying DDT inside homes to
attack mosquitoes that carry the disease, the
incidence dropped dramatically. By 1973, South
Africa recorded only 331 malaria cases in the
entire country, in 1977 a single death. DDT was
phased out by industrialized countries-including
South Africa-starting in the mid-1970s in favor
of the more expensive insecticides called
pyrethroids. But mosquitoes have developed
resistance to these compounds, and malaria is
again rampant throughout poor and politically
unstable regions of Asia, South and Central
America, and sub-Saharan Africa. The WHO says
malaria affects up to 500 million people per year
and kills about 2.7 million of them, mostly
children in sub-Saharan Africa. The South
African government has renewed DDT spraying, and
malaria cases are dropping. But the back lash
has created total uproar. The South Africans say
if they dont use DDT
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they will have a pandemic disaster. In December
2000 to the beginning of 2001 representatives of
more than 100 nations finalized a UN proposal to
impose a prohibition or gradual phase out of 12
substances including DDT. The group of 12
chemicals many of them chlorinated hydrocarbons
are known as POPs (persistent organic
pollutants). Malaria specialists have no quarrel
with banning such compounds as chlordane,
heptachlor, dieldrin, PCBs, and dioxin that have
been linked to cancer and damage to the human
nervous, reproductive, and endocrine system. But
they argue that DDT is benign in minute
quantities necessary to repel mosquitoes. Some
two dozen poor nations, and China and India,
continue to spray inside buildings. Preventing
poor countries from using DDT, they believe
smacks of eco-colonialism by rich countries more
concerned with theoretical long-term risks to
their own environment than with sickness and
death in the Third World. They also call this
another instance of First World values being
imposed globally, regardless of the consequences.

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Cl
H
2-monochlorobiphenyl
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209 congeners (distinct formulations) of which 23
seem to be environmentally important.
PCBs are a diverse group of organo-chlorines
consisting of a biphenyl ring with 10 available
positions for chlorination. In general, the
half-life of PCBs in the body increases with
increasing chlorination, and values have been
estimated to range from lt1 year to 71 years.
However, the most common congeners to which the
general population is exposed are characterized
by half-lives of 2-6 years. Thus, it may be
difficult to determine the complete historical
exposure to PCBs, as biological measurements are
often collected many years after exposures have
occurred. Ingestion of contaminated food
products, especially contaminated sport-caught
fish, is among the most important pathways of
exposure to PCBs. Reproductive factors, including
parity and breast-feeding, appear to decrease
body burdens of PCBs in reproductive-age women.
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PCBs - Polychlorinated Biphenyls

• 1922 Theodore Swann of the Federal Phosphorus
  Company set up a plant to produce biphenyl for
  use in heat transfer applications
• 1929 Swann developed PCBs
• 1930 Monsanto took over production of PCBs which
  they sold under the name of AROCLOR
• 1943 It was reported in an internal Monsanto
  memo that chlorinated naphthalene and biphenyl
  were generally highly toxic and should be used
  with extreme caution
• 1966 Dr. Soren Jensen an analytical chemist with
  the Univ. of Stockholm discovered PCBs in
  environmental samples while looking for DDT

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• 1970 Monsanto restricted the sale of PCBs to
  closed system manufacturers. GE capacitors
• 1977 Monsanto discontinued production of PCBs
• PCBs were found in significant quantities in
• Transformers and capacitors
• Heat transfer applications
• Washable wall coverings
• Coatings for ironing board covers
• Waterproofers and canvas
• File casting solutions
• Insulating tapes and protective lacquers
• Epoxy resins
• Carbonless carbon paper
• Hydraulic fluids
• Plasticizers
• DDT 1973 banned for sale in US

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• Sold under the name Aroclor as Aroclor 1254,
  Aroclor 1220, etc. where the second part of the
  number indicates the percent chlorination of the
  molecule, the higher the number the more
  chlorinated the molecule.
• PCBs are almost everywhere in the US
• The U.S. EPA calculated that 91 of all Americans
  have detectable levels of PCBs in their bodies,
  and 40.3 have at least 1 ppm
• The milk of nursing mothers had detectable levels
  of PCBs in all samples tested. The average 1.8
  ppm gave an infant seven times the amount the FDA
  permitted in cows milk.
• Many of the fish stocks of the Great Lakes and
  numerous of the nations river systems became too
  contaminated to eat because they contained more
  than 2 ppm (the limit set by the Federal
  Government controlling the number of fish that
  should be eaten by individuals).

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• Up to 20 ppm of PCBs have been found in fish from
  Lake Ontario, far higher than the 2 ppm set by
  the FDA. Laboratory animals have demonstrated a
  wide variety of adverse effects of PCBs in
  laboratory animals, including interference with
  reproduction, loss of hair, liver ailments, and
  gastrointestinal lesions.
• Dr. James Murphy estimated that almost half of
  the PCBs which contaminate Lake Michigan were
  entering the lake through precipitation.
• In New York, Michigan, and Texas companies
  (mid-night dumpers) drained PCBs from
  transformers, mixed it with crankcase oil and
  sold the mixture as a dust suppressor for dirt
  roads. Executives of these companies were
  sentenced to prison for these activities.

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• In another case PCBs in 55 gallon drums were
  buried in semi-trailers by companies collecting
  PCBs from industries for disposal. The
  collection companies would then dig a ditch, back
  the semi-trailer into the ditch, remove the
  tractor, and then bury the trailer and its
  contents. Big profits if you dont get caught.
  Cradle to grave. Newer laws
• In the fall of 1981, New York state hunters were
  warned to limit their consumption of wild ducks
  because of PCB contamination, Montana hunters
  were given the same warning for contamination by
  Endrin. Dissection of ducks from the Hudson
  River and Lake Ontario showed contamination
  levels as high as 7.5 ppm PCBs compared to the 2
  ppm limit. It was suggested that no more than
  two meals of ducks be eaten a month and the skin
  and fat should be carefully removed. If dressing
  was fixed with the ducks it was recommended that
  it should not be eaten.

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• In New York the striped bass fishery had to be
  shut down (shut down in 1976). Fish and
  sediments in the upper Hudson River were highly
  contaminated with PCBs. The source was traced to
  two closed system manufacturing plants owned by
  GE that made capacitors. Both facilities had
  discharge permits from the New York State
  Department of Conservation. The dilemma of the
  DOC was how to handle the contaminated sediments.
  The ultimate decision was to leave them in
  place, the rationale being that resuspending the
  fines during dredging would be more detrimental
  than leaving them in place. GE was fined and the
  DOC contributed some money to study the problem.
  The amount contributed by both was only about 20
  of the estimated costs to clean it up. The
  fishery is still shut down as of 2006.
• The first decision to remediate this problem was
  to allow the natural sediment to cover the
  contaminated areas.

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• Wednesday Dec. 6, 2000 EPA proposes a
  comprehensive plan to clean up the Hudson River
  and protect public health. The proposal came
  after 10 years of study. The proposal targets the
  most contaminated portion of the river and
  dredging is the recommended option. The plan
  recognizes the need for stepped up containment of
  new PCB contamination from active sources. The
  clean up would remove 100,000 pounds of PCBs that
  would potentially contaminate people, fish, and
  wildlife throughout the region. It would reduce
  health risks and fish contamination by five times
  immediately following clean-up. The PCB
  contamination dates back some 30 years ending in
  1977 during which GE discharged some 1.3 million
  pounds of PCBs directly to the river from its
  facilities in Hudson Falls and Fort Edward, New
  York.

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• EPA has extensive experience with dredging
  projects. The proposed clean-up plan calls for
  dredging the most contaminated areas about 12 of
  the 40-mile stretch of the Upper Hudson River.
  The plan calls for the removal of over 2.65
  million cubic yards of contaminated sediment,
  containing 150,000 lbs of total PCBs. Backfilling
  with clean material, then disposal and on-going
  monitoring. After treatment the dredged material
  would be transported away from the river (outside
  the Hudson River watershed)communities by rail
  for disposal. The dredging project, which would
  require GE to pay for it under Superfund law,
  would take an estimated five years and cost about
  460 million.

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EPA and GE have encountered multiple delays and
the project is now scheduled to begin in 2009.
With each year of delay another 500 pounds of
PCBs wash downstream, over the Federal Dam at
Troy to the lower Hudson River, an area that will
not be remediated under this clean up. After
more than three years of negotiations, on October
6, 2005 a Consent Decree was reached between GE
and EPA. Unfortunately this agreement, contrary
to the Record of Decision, allows GE to opt out
of the clean up after the first phase or only 10
percent of the remediation is complete.
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• Short-cakes in the Mid-west were found to contain
  PCB contamination.
• Cattle in Kansas

Zebra mussels (Dreissena polymorpha) invaded the
Hudson River in about 1990 and are abundant where
suitable habitat is found. Especially high
average densities (17,000/m2) are found on rocks
in waters deeper than 5 m. Zebra mussels have had
a profound effect on the ecosystem. Resent
estimates suggest that the zebra mussel
population of the lower Hudson River may filter a
volume of water equal to the entire volume of the
tidal freshwater river every 2 days, altering the
planktonic community. I addition a recent summer
time decline in dissolved oxygen levels can be
attributed to the arrival and spread of the zebra
mussels. Much research remains to be done on how
or if the zebra mussel influences the dynamics of
PCB bioaccumulation and transfer through the
Hudson River ecosystem.
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Characteristics of PCBs Class of
chemicals Naturally occurring? Synthetic or
Manmade? Bioaccumulate Bioconcentrate Biomagnify H
ydrophilic Hydrophobic Lipophilic Lipophobic
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Two New Reports Show Industrial Toxins in Human
Bodies- World Watch Nov/Dec 2005 Heavy metals,
pesticides, solvents, fire retardants, glues,
coatings, and combustion emissions are just some
of the pollutants absorbed into our bodies on a
daily basis, according to two recent studies on
human exposure. In the National Report on Human
Exposure to Environmental Chemicals, researchers
at the U.S. Centers for Disease Control and
Prevention (CDC) tested the blood and urine of
2,400 Americans for 148 common chemicals. Among
the pollutants found in high levels were cadmium,
a heavy metal thought to be absorbed from
cigarette smoke and associated with weakened
bones and kidney injuries, and phthalates, common
plastic softeners that have been linked to
diminished reproductive functioning. Although
most of the chemicals the CDC tested for existed
in concentrations below those believed to be
debilitating, the report emphasized the dearth of
knowledge about chronic exposure to toxins. On
the plus side, the researchers pointed to
declines in Americans exposure to lead sources
such as old paint and to more stringent limits on
public smoking. And what else..?
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A second study, by the Environmental Working
Group (EWG), tested for 413 different pollutants
in the umbilical blood of 10 newborn babies. Of
the 287 chemicals that were present, 180 are
known to cause cancer in humans or animals
(hmmmmm OR.). 208 have been shown to contribute
to developmental problems, and 217 are toxic to
the nervous system. Although embryologists once
believed that the placenta protected babies in
the womb, they now know that many toxins can
filter through, threatening fetuses and newborn
babies during sensitive stages of
development. Citing pervasive ignorance about the
75,000 chemicals currently manufactured in or
imported into the U.S., EWG advocated a more
precautionary approach to chemical use. It
recommended that the U.S. EPA be given more
leeway in demanding safety assessments and that
chemical manufacturers be required to demonstrate
the safety of their products in the womb.
Consumers can also reduce their personal risk by
eating organic foods, maintaining a pesticide
free household, and limiting use of hygiene
products such as hair sprays, cosmetics, and
deodorizers.
Precautionary principle, 75,000 chemicals, etc.
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January 30, 2008 Government promises to rid the
nations food supply of brain-damaging pesticides
arent doing the job according to the results of
a yearlong study that carefully monitored the
diets of a group of local children. The peer
reviewed study found that the urine and saliva of
children eating a variety of conventional foods
from area groceries contained biological markers
of organophosphates, the family of pesticides
spawned by the creation of nerve gas in World War
II (in this study malathion and chlorpyrifos).
Overall pesticide marker levels in urine samples
were even higher in the winter months, suggesting
children may have consumed fruits and vegetables
that were imported. The government needs to
ensure that imported food comply with the
standards we impose on domestic produce. Once
you switch from conventional food to organic, the
pesticides that the authors can measure in the
urine disappear. The level returns immediately
when you go back to the conventional diets. Death
or serious health problems have been demonstrated
in thousands of cases in which there were
high-level exposures to malathion and
chlorpyrifos. But a link between neurological
impairments and low-level exposure is far more
difficult to determine.
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The lead author on this study is Professor Lu
from Emory University and a member of US EPAs
pesticide advisory panel. He stated in a press
release regarding this peer reviewed journal
article, It is appropriate to assume that if we
human beings are exposed to this class of
pesticides, even though its a low-level exposure
on a daily basis, there are going to be some
health concerns down the road. There is a
large underpinning of animal research for
organophosphate pesticides, and particularly for
chlorpyrifos, that points to bad outcomes in
terms of the effects on brain development and
behavior. Dr. Theodore Slotkin, a professor of
pharmacology and cancer biology at Duke
University. Congressional concern that children
were being harmed by excessive exposure to
pesticides led to the unanimous passage of the
Food Quality Protection Act. At its heart was a
requirement that by 2006, the EPA complete a
comprehensive reassessment of the 9,721
pesticides permitted for use and determine the
safe level of pesticide residues permitted for
all food products. Handout
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CH3
C
N
CH
CH3
OC2H5
C
C
O
P
CH
OC2H5
N
CH3
S
What have we done to replace things like DDT? One
class of chemicals has been developed called
organophosphates. Of which Diazinon shown above
is an example. O,O,-Diethyl
O-(2isopropyl-4-methyl-6-pyrimidinyl)
phosphorothioate Acetylcholinesterase inhibitor
Action insecticide and nematicide Use For
soil insects and pests of fruits, vegetables,
tobacco, forage, field crops, range, pasture,
grasslands, ornamentals. For cockroaches and
other household insects including grubs,
nematodes in turf, seed treatment and fly
control.
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How many containers 100 yds long x 50 yards wide
x 3 yards deep would it take to dilute the
diazinon in a quart container of 25 diazinon by
weight to the recommended concentration of 80
ng/L. Conversions To Convert From To
Multiply by gm mg 1,000 mg ug 1,000 ug
ng 1,000 ml gm 1 cc ml 1 qt ml 9
46.33 liters gallons 0.26417205 gallons ft3
0.13368 ft3 yd3 3.7037x10-2
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Diazinon Safe concentration for aquatic life is
80 ng/L although newer research indicates that it
might be as low as 8 ng/L. The concentration in
25 diazinon is 25 by weight. One liter
contains ___________ ml, and weighs
________________ gms. One quart contains
_____________ ml, therefore a quart weighs
________? If one quart weighs ____________ gms
and 25 of that is diazinon then one quart
contains ________________ gms of
diazinon _____________ gm of diazinon
________________ mg of diazinon _____________ mg
of diazinon ________________ ug of
diazinon _____________ ug of diazinon
_________________ ng of diazinon How many liters
need to be added to the solution containing
________ ng of diazinon to reduce it to 80 ng/L?

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__________________ ng 80 ng/L x
___________________ liters x To
convert liters to gallons multiply by ___________
____________ To convert gallons to ft3 multiply
by ___________ _____________ One yd3
contains 27 ft3 to convert ft3 to yd3 divide by
27 __________ How many containers 100 yds long
by 50 yds wide x 3 yds deep does it take to
dilute the amount of diazinon in a quart or 25
diazinon to 80 ng/L? If it turns out that the
safe concentration is 8 ng/L how many boxes
would it take?
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Whats Happening with Diazinon Outdoor Use
Products? As part of an agreement between U.S.
EPA and diazinon manufacturers to phase out and
eliminate all residential uses of the insecticide
diazinon, retailers can no longer sell diazinon
outdoor non-agricultural use products, including
home lawn and garden products, after December 31,
2004. It will be illegal for retailers to sell
these products after that date. However,
consumers may continue to use diazinon products
purchased before that date, provided they follow
all label directions and precautions.
What are my Options as a Retailer? Diazinon
manufacturers will repurchase from retailers for
formulators any unopened, unused supplies of
diazinon outdoor non-agricultural use products
after December 31, 2004, and before March 31,
2005. If you have questions or need additional
information, contact your distributor.
RUP. Or. RIP?
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Perform a toxicity test on copper starting with
CuSO45H2O we Need to prepare a 10 mg/L solution
of copper.
What do we need to know
Atomic weights of each of the elements and the
number of each of the elements
x 39.292 mg of CuSO45H2O gives a nominal 10
mg/L solution of Cu
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Biomonitoring

• Using biological material to monitor for the
  presence of toxicants
• No instrument has yet been made that can measure
  toxicity! Chemical concentrations can be measured
  but only living material can be used to measure
  toxicity.

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History Although most of the poisons of the time
were of vegetable origin, the sulfide of arsenic
and arsenious acid were known to be used. It has
been postulated that arsenic was the poison with
which Agrippina killed Claudius to make Nero,
Emperor of Rome. This postulate is supported by
the later used of the same material by Nero in
poisoning Britannicus, Claudius natural son.
The deed was done under the direction of Locusta,
a professional poisoner attached to the
family. The mixture of fact and legend that
surrounds the murder illustrates the practices of
the times. A first attempt to kill Britannicus
failed but the illness reported contained
evidence of all the symptoms of arsenic
poisoning. The failure led to suspicion and
Britannicus family hired a taster (biomonitor).
The second, successful, attempt involved a more
devious scheme. The arsenic had been placed in
cold water and Britannicus was served excessively
hot soup. The taster had demonstrated the safety
of the soup but it was not retested after the
water had been added to cool the soup.
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Here superstition and legend embellish the story.
Nero claimed that Britannicus had died of
epilepsy and ordered his immediate burial to
prevent others from seeing the blackening of the
body believed to occur after poisoning. As the
legend has it the corpse was painted with
cosmetics to hide the deed, but in a raging rain
storm the cosmetics were washed off, revealing
Neros evil deed. Tasters are one type of
biomonitor.. What do you see as its strengths
and weaknesses? Name another biomonitor from
history?
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When in Rome Do as the Romans Do From all one
reads you get the sense that the Romans liked a
good party. Clearly the infrastructure of the
Roman Empire was well advanced. The Romans had
gone so far as to develop a system to transport
sewage. There are a lot of theories about the
downfall of the Roman Empire. One of those
theories, which is considered by scholars as a
reasonable one is of toxicological origin. Does
anyone know what that theory might be?
California popytrail coke in pottery etc.
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Antagonism and Bioavailability It is clear that
the Greeks and Romans made considerable use of
poisons, often political. Much legend and myth
has grown out of the skill of poisoners and the
occupational hazards of political life during the
period. One such legend tells of King
Mithridates of Pontus, who was so fearful of
poisons that he regularly ingested a mixture of
36 ingredients (Galen says it was 54 ingredients)
as protection against assassination. On the
occasion of his imminent capture by his enemies,
his attempt to kill himself with poisons failed
because of his successful concoction and he was
forced to use his sword held by a servant. From
this tale comes the term mithridatic referring
to an antidotal or protective mixture.
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Additivity, Antagonism, Synergism Assume one
unit of toxicant 1 causes 50 mortality of a test
species exposed to it and 1 unit of toxicant 2
causes 50 mortality of the same test species
exposed to it. Additivity If these two
toxicants are strictly additive then, 0.5 units
of toxicant 1 mixed together with 0.5 units of
toxicant 2 should cause 50 mortality to the same
test species. Antagonism If these two toxicants
are antagonistic to one another then 0.5 units of
toxicant 1mixed with 0.5 units of toxicant 2
should kill less than 50 of the same test
species. Synergism If these two toxicants are
synergistic to one another then 0.5 units of
toxicant 1 mixed with 0.5 units of toxicant 2
should kill more than 50 of the same test
species, i.e. the toxicants facilitate one
another.
48
La Voisin Early Toxicologist The culmination
of the practice of poisoning in France is
represented by the commercialization of the
service by Catherine deShayes, who earned the
title of La Voisin before she was
decapitated. Under the guise of delivering care
to the sick and poor, Catherine tested toxic
concoctions, carefully noting the rapidity of the
toxic response (the onset of action), the
effectiveness of the concoction (potency), the
degree of responses of the parts of the body
(specificity or site of action), and the
complaints of the victim (clinical signs and
symptoms). Clearly Catherine must be given
credit as perhaps the earliest untrained
toxicologist. Her business was dissolved by her
execution. Her trial was one of the most famous
of those held by the Chambre Ardente, a special
judicial commission established by Louis XIV to
try such cases with out regard to age, sex, or
national origin. La Voisin was convicted of
many poisonings, including over 2,000 infants
among her victims.
49
Dose - Response
Typical frequency distribution for the tolerance
concentrations of a population. The area between
any two ordinances represents the proportion of
subjects having tolerances between those two
concentrations.
50
Sigmoid curve derived from Typical Frequency
Distribution Curve showing the percentage of
insects with tolerances less than a specified
concentration.
51
The LC50 is ___________ ?
Normal sigmoid curve derived from the Typical
Frequency Distribution Curve showing percentage
of insects with log-tolerances less than a
specified concentration.
52
log normal curve
Normal frequency distribution for the logarithms
of the tolerance concentrations shown in the
Typical Frequency Distributions of a population.
53
Not all chemicals are acutely toxic and not all
chemicals cause death. Some chemicals may alter
behavior.
54
Copper Calculations In 1864, the composition
of the cent was set at 95 copper and 5 tin and
zinc and its weight was reduced to 48 grains (to
convert grains to milligrams multiply grains by
64.79891). In 1943 a steel-zinc combination
penny was minted and in 1962 the alloy was
changed to 95 copper and 5 zinc. The rising
cost of copper lead Congress to authorize a coin
that was 97.6 zinc and 2.4 copper but such
pennies were not minted in quantity until
1983. Weight of penny 2.4833 grams How many
grams are copper are there in a penny that weighs
2.4833 grams? The Gold Book of Water Quality
states that The procedures described in the
Guidelines for Deriving Numerical Water Quality
Criteria for the protection of Aquatic Organisms
and Uses indicate that, except possibly where a
locally important species is very sensitive,
freshwater aquatic organisms and their use should
not be
55
affected unacceptably if the 4-day average
concentration in (ug/L) of copper does not
exceed the numerical value given by
e(0.8545ln(hardness)-1.465 more than once
every three years on the average and if the one
hour average concentration (in ug/L) does not
exceed the numerical value given by
e(0.9422ln(hardness)-1.464 more than once
every three years on average. For example, at
hardnesses of 50, 100, and 200 mg/L as CaCO3 the
four day average concentrations of copper are
6.5, 12, and 21 ug/L respectively, and the 1 hour
average concentrations are 9.2, 18, and 34 ug/L.
What quantity of water would be required to
reduce the concentration of copper in a dissolved
penny to 6.5 and 9.2 ug/L respectively. _______
______ug 9.2 ug/L
x liters How many gallons is
that? To convert liters to gallons multiply by
0.26417205
56
Malathion Label Use For many insects
including aphids, spider mites, scale insects,
house fly, and mosquitoes as well as a large
number of sucking and chewing insects attacking
fruits, vegetables, ornamentals, and stored
products. Adult mosquito control in public
health programs. Particularly where a high
degree of safety to mammals is desired a
tolerance of 135 ppm for forage, grass, and green
hay allows malathion to be applied the same day
as grazed or harvested. Generally established
tolerances for residues of 8 ppm malathion.
There are specialized uses with higher and lower
tolerances. Fyfanon ULV (ultra-low volume spray)
for most major uses. Malathion ULV Concentrate
for ultra-low volume aerial application to
alfalfa, clover, pasture, and range grasses,
nonagricultural land, cereal crops, cotton, when
it can be diluted with vegetable oil and applied
ULV, safflower, soybeans, sugar beets, corn,
beans, blueberries for the control of many
insects at rates of 4-16 ounces per acre.
57
Formulations Dust, emulsifiable, oil solutions,
powder, ULV concentrate, wettable
powder. Malathion Label Hazards to Humans and
Domestic Animals Warning Harmful is swallowed,
inhaled, or absorbed through the skin. Avoid
breathing spray mist. Causes eye irritation. Do
not get in eyes, skin, or clothing. Wash skin
with plenty of water while removing contaminated
clothing before reuse. Statement of Practical
Treatment If swallowed, do not induce
vomiting. Get medical attention. In case of
contact, immediately flush eyes and skin with
plenty of water while removing contaminated
clothing and shoes. Call a physician. Wash
clothing before use. NOTE TO PHYSCIAN Atropine
is antidotal. 2-PAM may be effective as an
adjunct to atropine.
58
In the U.S. (2007) there are currently 1282
products on the market containing malathion.
59
1995 dated. Other chemicals suspected of
causing testicular cancer and dysfunction in dogs
and humans who served in Vietnam are the
antibiotic tetracycline and the pesticide
malathion. Many military dogs in Vietnam suffered
from ear infections and other diseases.
17Therefore, many received one or more doses of
tetracycline during their tour of duty.
Tetracycline is strongly absorbed by sperm in
mammals, and is known to cause testicular atrophy
(shrinkage), and diminished sperm quality in
humans and dogs. The other suspicious candidate
is malathion. The same military unit that sprayed
Agent Orange also sprayed DDT and malathion
extensively in the vicinity of U.S. troops, to
reduce the dangers of malaria carried by
mosquitoes. It has been reported that 44 of the
land of southeast Asia, mainly Vietnam, was
sprayed with malathion during the war.
18Furthermore, military working dogs in Vietnam
were dipped in a 0.5 solution of malathion to
kill disease-carrying ticks. Malathion is known
to cause testicular atrophy and damage to the
sperm-generating cells of laboratory animals.
19 Malathion is widely use throughout the U.S.
today for mosquito control though not for fear of
malaria. Mosquitoes are simply a nuisance. EPA
estimates that 4 to 6 million pounds (1.8 to 2.7
million kilograms) of "active ingredient" of
malathion are sprayed in the U.S. each year. The
yearly total of malathion formulation sprayed is,
again, 20 to 200 times this amount. Sperm count
in men throughout the industrialized world
appears to be dropping. (See RHWN 343 and 432.)
Testicular cancer is the most prevalent cancer
among white males between the ages of 25 and 34
years and the second most common in the 35-to-39
age group. The causes of testicular cancer are
thought to be environmental because the rates
vary widely from one location to another. During
the last 15 years, the rates have increased
rapidly (2.3 to 3.4 per year) in many
industrialized countries. 20
60
Environmental Hazards This pesticide is toxic to
fish, aquatic invertebrates, and aquatic life
stages of amphibians. Do not apply directly to
water or wetlands (i.e., swamps, bogs, marshes,
and potholes). Drift and runoff may be hazardous
to aquatic organisms near an application site.
Do not contaminate water when disposing of
equipment washwaters. This product is highly
toxic to bees exposed to drift to blooming crops
or weeds if bees are visiting the treatment area.
Storage Store in a locked storage area out of
the reach of children and domestic animals. Do
not store near heat or open flame. Leave in
original container until used. PESTICIDE
DISPOSAL Unwanted pesticide material leave in
the original container, wrap in several layers of
newspaper and discard in trash. CONTAINER
DISPOSAL Do not reuse the container. Rinse
thoroughly before discarding in trash.
Restricted Use Pesticides .. Environmental Risk
Assessment PEC and PNEC Ratio PEC/PNEC PIC
(prior informed consent) Emergency Exemption
Process
61
Malathion The water quality criterion for
Malathion is 0.1 ug/L or 100 ng/L. This number
was derived by applying an application factor of
0.1 to the 96-hour LC50 data for Gammarus
lacustris, G. fasciatis, and Daphnia, which are
approximately 1.0 ug/L. The concentration of 50
Malathion is 50 by weight. How many football
field sized containers 100 yds long x 50 yds wide
x 3 yds deep would it take to dilute the
concentration of malathion in a quart container
of 50 Malathion to 100 ng/L.
62
The water quality criterion for Malathion is 0.1
ug/L or ___________ ng/L. The concentration of
Malathion in 50 malathion is 50 by weight. One
liter contains _____________ gms of malathion.
One quart contains _____________ gms of
malathion. Therefore, one quart of malathion
contains ________ gm of malathion, or
___________ mg or _____________ ug or
___________ng of malathion. How many liters
would it take to dilute ___________ ng of
malathion to 100 ng/L ______________________? A
football field is 100 yds long (excluding the
endzone), and 50 yards wide if it were 3 yards
deep how may cubic yards would it hold
_____________________? How many football field
sized containers 3 yards deep would it take to
dilute the concentration of malathion in 1 quart
sized container of 50 malathion to 0.1 ug/L?
___________________

63
To Convert From To Multiply by gm mg 1000
mg ug 1000 ug ng 1000 ml gm 1 cc ml
1 cc gm 1 qt ml 946.333 liters
gallons 0.2642 gallons ft3 0.13 ft3 yd3
3.7037x10-2