lecture 22008

8/6/2019 Lecture 22008

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Sink Source

Benthic

Epi-benthic

Water

Bedrock

Air

Sediments

Point Source

Non-Point

Source

Ground water

Hyporheic zones

Biota

Microlayer

Chemical Fate

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Sink Source

Benthic

Epi-benthicSurficial

SedimentsSediment

Water

Bedrock

Bedrock

inorganicorganic

Chironomid

larvae

pore water

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C

CCl Cl

Cl

H

ClCl

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 frequentlydetected pesticide on produce entering the U.S.

� Prior to its being banned DDT was accumulatingin the fat of humans and all other animalsincluding Arctic seals, and Antarctic penguinseven though these animals were far removed from

any point of application. Further study showedthat birds were acquiring high levels of DDT bybiomagnification

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� DDT was classified as a suspected occupational

carcinogen that should be handled cautiously inthe workplace.

� Statistically significant correlation between high body burdens of DDT and breast cancer wereobserved. (Correlation does not establish causeand effect, There is a significant correlationbetween the number of Baptist ministers in aCity and liquor consumption.)

� At a site in California people found DDT the size

of bowling balls under houses surrounding the sitethat was abandoned by a chemical company still in business. EPA bought the homes. Sewers leadingto 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 thatcontinue 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 SuperfundLaw, 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 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 thatconveyed 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 continuesfor 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 soybeansaccount 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, andcemeteries. 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 1960¶s DDT was sprayed on the thatched roofs andvegetation 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-startingin 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 don¶t 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 withtheoretical 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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ClHH H H

HH

H H H H

23

4

5 6

2¶ 3¶

4¶

5¶6¶

Cl Cl

ClCl

ClCl

Cl Cl

ClCl

2,2¶3,3¶4,4¶5,5¶6,6¶-decachlorobiphenyl

2-monochlorobiphenyl

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209 congeners (distinct formulations)

of which 23 seem to be environmentallyimportant.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 commoncongeners 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, isamong 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 PhosphorusCompany set up a plant to produce biphenyl for use in heat transfer applications

� 1929 Swann developed PCBs

� 1930 Monsanto took over production of PCBswhich they sold under the name of AROCLOR

� 1943 It was reported in an internal Monsantomemo that chlorinated naphthalene and biphenyl

were generally highly toxic and should be usedwith extreme caution

� 1966 Dr. Soren Jensen an analytical chemist withthe Univ. of Stockholm discovered PCBs in

environmental samples while looking for DDT

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� 1970 ± Monsanto restricted the sale of PCBs toclosed 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 indicatesthe 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 havedetectable levels of PCBs in their bodies, and 40.3% haveat least 1 ppm

� The milk of nursing mothers had detectable levels of PCBsin all samples tested. The average 1.8 ppm gave an infantseven 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 toeat because they contained more than 2 ppm (the limit set by the Federal Government controlling the number of fishthat should be eaten by individuals).

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� Up to 20 ppm of PCBs have been found in fishfrom Lake Ontario, far higher than the 2 ppm set by the FDA. Laboratory animals havedemonstrated a wide variety of adverse effects of PCBs in laboratory animals, including interferencewith reproduction, loss of hair, liver ailments, andgastrointestinal lesions.

� Dr. James Murphy estimated that almost half of the PCBs which contaminate Lake Michigan wereentering the lake through precipitation.

� In New York, Michigan, and Texas companies

(mid-night dumpers) drained PCBs fromtransformers, mixed it with crankcase oil and soldthe 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 insemi-trailers by companies collecting PCBs from

industries for disposal. The collection companies wouldthen dig a ditch, back the semi-trailer into the ditch,remove the tractor, and then bury the trailer and itscontents. Big profits if you don¶t get caught. Cradle tograve««. Newer laws

� In the fall of 1981, New York state hunters were warned tolimit their consumption of wild ducks because of PCBcontamination, Montana hunters were given the samewarning for contamination by Endrin. Dissection of ducksfrom the Hudson River and Lake Ontario showed

contamination levels as high as 7.5 ppm PCBs compared tothe 2 ppm limit. It was suggested that no more than twomeals of ducks be eaten a month and the skin and fatshould 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 facilitieshad discharge permits from the New York StateDepartment of Conservation. The dilemma of the DOCwas 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 bemore detrimental than leaving them in place. GE was finedand 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 isstill shut down as of 2006«.

� The first decision to remediate this problem was to allowthe natural sediment to cover the contaminated areas.

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� Wednesday Dec. 6, 2000 ± EPA proposes acomprehensive 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 portionof 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 upwould remove 100,000 pounds of PCBs that would

potentially contaminate people, fish, and wildlifethroughout the region. It would reduce health risks andfish contamination by five times immediately followingclean-up. The PCB contamination dates back some 30years ending in 1977 during which GE discharged some

1.3 million pounds of PCBs directly to the river from itsfacilities 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 millioncubic yards of contaminated sediment, containing150,000 lbs of total PCBs. Backfilling with clean

material, then disposal and on-going monitoring.After treatment the dredged material would betransported away from the river (outside theHudson River watershed)communities by rail for

disposal. The dredging project, which wouldrequire 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 ³opt 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 PCBcontamination.

�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 onthe 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 timedecline 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

Hydrophilic

Hydrophobic

Lipophilic

Lipophobic

Cl Cl

ClCl

ClCl

Cl Cl

ClCl

2,2¶3,3¶4,4¶5,5¶6,6¶-decachlorobiphenyl

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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 N ational 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 tochemical 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, anddeodorizers.

Precautionary principle, 75,000 chemicals, etc.

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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 evenhigher 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 immediatelywhen 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 EPA¶s pesticide advisory panel. He stated in a press release

regarding this peer reviewed journal article, ³It is appropriate to assume

that if we ± human beings± are exposed to this class of pesticides, eventhough it¶s a low-level exposure on a daily basis, there are going to be

some health concerns down the road.´

³There is a large underpinning of animal research for organophosphate

pesticides, and particularly for chlorpyrifos, that points to bad outcomes interms 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 excessiveexposure 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

CH3

CH3

C

N CH

C C

N

O P

S OC2H5

OC2H5

CH

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,-DiethylO-(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 1,000ug 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

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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 diazinonthen 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 ³safe´ concentration is 8 ng/L how many boxeswould it take?

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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 andgarden 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 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++

x 10

x = 39.292 mg of CuSO4�5H2O gives a nominal 10 mg/L solution of Cu++

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Biomonitoring� Using biological material to monitor for the

presence of toxicants

� ³No 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 ataster (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 Nero¶s 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 alot 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 hasgrown 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 36ingredients (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 hewas forced to use his sword held by a servant. From this

tale comes the term ³mithridatic´ 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 then0.5 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.

L V i i E l T i l i

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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.

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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.

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Sigmoid curve derived from Typical Frequency Distribution

Curve showing the percentage of insects with tolerances less than

a specified concentration.

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Normal sigmoid curve derived from the Typical Frequency

Distribution Curve showing percentage of insects with log-

tolerances less than a specified concentration.

The LC50 is ___________ ?

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Normal frequency distribution for the logarithms of the tolerance

concentrations shown in the Typical Frequency Distributions of a

population.

log normal curve

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Not all chemicals are acutely toxic and not allchemicals cause death. Some chemicals mayalter behavior.

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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

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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 averageconcentrations 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/Lx liters

How many gallons is that?

To convert liters to gallons multiply by 0.26417205

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Malathion Label

Use: For many insects including aphids, spider mites, scale insects,

house fly, and mosquitoes as well as a large number of sucking andchewing 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.

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Formulations: Dust, emulsifiable, oil solutions, powder, ULV

concentrate, wettable powder.

Malathion LabelHazards 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 whileremoving 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 removingcontaminated 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.

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In the U.S. (2007) there are currently 1282 products on the market

containing malathion.

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1995 dated«.

Other chemicals suspected of causing testicular cancer and dysfunction in dogs and humans who served inVietnam 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 withmalathion 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.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]

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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 organismsnear 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

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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 quartcontainer of 50% Malathion to 100 ng/L.

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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? ___________________

T C F T M l i l b

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To Convert From To Multiply by

gm mg 1000

mg ug 1000

ug ng 1000

ml gm 1

cc ml 1cc gm 1

qt ml 946.333

liters gallons 0.2642gallons ft3 0.13

ft3 yd3 3.7037x10-2

lecture 22008

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