Non-Point
Source
Microlayer
Air
Ground water
Hyporheic zones
Water
Source
Sink
Biota
Point Source
Epi-benthic
Sediments
Benthic
Bedrock
Chemical Fate
Water
Source
Sink
Surficial
Sediments
Epi-benthic
Benthic
Sediment
Bedrock
inorganic
organic
Chironomid
larvae
pore water
Bedrock
H
Cl
C
Cl
Cl C Cl
Cl
Dichlorodiphenyltrichloroethane
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
• 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.
• The California site is a superfund site (Superfund is the federal
government’s program to clean up the nation’s uncontrolled hazardous
waste sites) 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 Palos 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.
• Montrose Chemical Corp. Was the nation’s 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.
• 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 (northern Mariana Islands and Guam), Samoan,
Marshallese, and Tongan. Who says we are not a country
of emigrants.
• Handout ……..
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.
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). Example lead
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. Example DDT
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.
Characteristics of DDT (POP under Stockholm Convention of the U.N.)
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?
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 - mirex is one of the POPs
All things are connected
Reported by Dr. Paul Ehrlich
In the early 1960’s 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 then 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.
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
(chrysanthemum flowers). 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 subSaharan Africa. The WHO says malaria affects up to 500 million people
per year and kills about 2.7 million of them, mostly children in subSaharan 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 don’t use DDT
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.
Cl
H
H
3
H
H
2
H
2’
3’
4’
4
5
H
Cl
6
6’
H
H
5’
2-monochlorobiphenyl
Cl Cl
PCBs
H
H
Cl
Cl
Cl
Cl
Cl
Cl
Cl
2,2’3,3’4,4’5,5’6,6’-decachlorobiphenyl
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 <1 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 (number of times a female has given
birth) and breast-feeding, appear to decrease body burdens of PCBs in
reproductive-age women.
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
• 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
• 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 cow’s milk.
• Many of the fish stocks of the Great Lakes and numerous
of the nation’s 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).
• 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.
• 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 don’t 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.
• 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.
• 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.
• 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.
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.
•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.
Characteristics of PCBs
Class of chemicals
Naturally occurring?
Synthetic or Manmade?
Cl
Bioaccumulate
Cl
Cl
Cl
Bioconcentrate
Biomagnify
Cl
Cl
Hydrophilic
Hydrophobic
Lipophilic
Lipophobic
Cl
Cl
Cl
Cl
2,2’3,3’4,4’5,5’6,6’-decachlorobiphenyl
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……..?
DFS
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.
In the face of high levels of uncertainty act
conservatively.
January 30, 2008
Government promises to rid the nation’s food supply of brain-damaging
pesticides aren’t 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.
The lead author on this study is Professor Lu from Emory University and a
member of US EPA’s 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 it’s 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
CH3
C
N
CH
CH3
C
CH C
N
CH3
OC2H5
O P
OC2H5
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.
(Example and calculation)
USES
Diazinon is a non-systemic insecticide used in agriculture to
control soil and foliage insects and pests on a variety of fruit
vegetable, nut and field crops. Diazinon is also used on nonlactating cattle in an insecticidal ear tag. Prior to cancellation of
all residential uses in by 2004, diazinon was used outdoors on
lawns and gardens, indoors for fly control and in pet collars to
control fleas and ticks.
Diazinon is metabolized within organisms to form diazoxon
(sometimes referred to as “activation,) diazoxon is a more potent
cholinesterase inhibitor compared to diazinon itself.
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
946.33
liters
gallons
0.26417205
gallons
ft3
0.13368
ft3
yd3
3.7037x10-2
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?
__________________ 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?
What’s 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.
It was possible before diazinon was restricted to agricultural uses, that I could go
into the store and buy a one gallon container containing 50% diazinon!
RUP……. Or……. RIP?
Perform a toxicity test on copper starting with CuSO4•5H2O 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
Copper 63.546 x 1 = 63.546
Sulfur 32.066 x 1 = 32.066
Oxygen 15.9994 x 9 = 143.9946
Hydrogen 1.00794 x 10 = 10.0794
Sum
249.686 Formula Weight
249.686 mg of CuSO4•5H2O contains 63.546 mg of Cu++
10
x
x = 39.292 mg of CuSO4•5H2O dissolved in 1 liter of water gives a nominal 10
mg/L solution of Cu++
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.”
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.
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 Nero’s evil deed.
Tasters are one type of biomonitor….. What do you see as its
strengths and weaknesses?
Name another biomonitor from history?
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.
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.
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.
DFS
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.
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.
Sigmoid curve derived from Typical Frequency Distribution
Curve showing the percentage of insects with tolerances less than
a specified concentration.
The LC50 is ___________ ?
Normal sigmoid curve derived from the Typical Frequency
Distribution Curve showing percentage of insects with logtolerances less than a specified concentration.
log normal curve
Normal frequency distribution for the logarithms of the tolerance
concentrations shown in the Typical Frequency Distributions of a
population.
Not all chemicals are acutely toxic and not all
chemicals cause death. Some chemicals may
alter behavior.
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 steelzinc 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
affected unacceptably if the 4-day average concentration in (ug/L) of
copper does not exceed the numerical value given by
e(0.8545[ln(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(0.9422[ln(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
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.
Formulations: Dust, emulsifiable, oil solutions, powder, ULV
concentrate, wettable powder.
Malathion Label
Hazards to Humans and Domestic Animals
Warning: Harmful if swallowed, inhaled, or absorbed through the
skin. Avoid breathing spray mist. Causes eye irritation. Do not get
in eyes, on skin, or clothing. Wash skin with plenty of water while
removing contaminated clothing wash 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.
In the U.S. (2007) there are currently 1282 products on the market
containing malathion.
Note
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. [17]Therefore, 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. [18]Furthermore, 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. Birds carrying West Nile virus bitten by mosquito that in turn
bites a homo sapien.
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]
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
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 sp., 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.
My answer was 401 containers, see if you
can get this answer or another answer you
are comfortable with, i.e, you do it twice
and get the same answer…….
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? ___________________
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