PENTACHLOROPHENOL IN THE MISSISSIPPI RIVER GULF GUTLET PROBLEMS AND IMPLICATIONS

Nancy G. Maynard Hazardous Materials Response NOAA/OMPA RD MPF 29 325 Broadway mulder, Colorado 80303

Project

ABSTRACT
As

2.

PROBLEMS INVOLVEDWITH HAZARDOUS MATERIALS SPILLS

the transport of hazardous substances by The problems associated with hazardous materials water increases, the probability of accidental spills are far more significant than those of spills into the marine environment will grow accordingly. The problems associated with spills oil spills both in terms of human health of hazardous substances are far more serious than hazard and potential for environmental damage. oil spills both in terms of human health hazards In the first place, the kinds of substances and potential environmental damage. Tracking the spilled are so diverse and potentially dangerous, spread of an often invisible but possibly they have been divided into the following eight the physical and dangerous contaminant throughout general United Nations Classes of compounds for biological phases of the marine ecosystem is only (6). the purpose of quick hazard identification one of the major difficulties encountered in this type of spill. explosives gases (PCP) During a recent spill of pentachlorophenol flammable and combustible liquids into a ship channel in New Orleans, Louisiana, flammable solids many of the problems unique to hazardous materials oxidizers and organic peroxides were encountered and had to be addressed within poisons strict time constraints. This paper lists the radioactive materials most common problems encountered at hazardous corrosives B materials spills, briefly describes Pthe incident, and discusses implications of the Secondly, exposure to substances from these growing marine transport of hazardous chemicals to eight classes can lead to either immediate humans and their environment. health effects from fires, explosions, poisoning, contamination, suffocation, chemical bums, or delayed intensive heat and extreme cold 1 . INTRODUCTION health effects from such causes as infectious organisms, pathogenic organisms, irritants, bioThe manufacture, transport, storage, use, and accumulation, mutagens, carcinogens, teratogens, disposal of hazardous materials have increased poisons, and corrosives. It is obvious, theredramatically over the past twenty-five years. In from hazardous fore, that the damage potential the United States alone, production of synthetic materials to the health and welfare of humans . 3 billion organic chemicals has increased 3 from as well as to the environment is immense. (1). pounds in 1939 255 to billion pounds in 1977 Over 3,000 spills of hazardous materials into As part of a safe and effective response to navigable waters are now estimated to occur each spilis of hazardous materials, a number of year (14), ranging in size from a few millimeters critical questions must be asked in order to (2). to billions of liters insure that all of the potential problems associated with such spills are addressed. Most Unique and potentially dangerous problems are of the management/scientific questions are presented by spills of hazardous materials whichsimilar to those questions formulated sysfor threaten the health and welfare of both humans and tematic response to oil spills although they the environment. Some of these problems were have been modified to fit the difficulties of encountered duringa recent spill of a derivative hazardous materials (9,lO) However, deriving of one of the most commonly spilled hazardous quick and accurate answers to these questions materials. Over 12 tons of the phenols, pentaduring a spill response requires a highly chlorophenol (PCP), was spilled into the Missis- organized response system which includes a 20 miles southeast of New complete pre-spill evaluation of the many sippi River Gulf Outlet July of 1 9 8 0 . A brief Orleans, Louisiana, in diverse and dangerous problems associated of some with hazardous materials. Ten of the most synopsis of the spill incident is given, the typical problems of hazardous materials frequently asked spill questions are listed spills are listed, and implications of the in Table1 and the many problems associated ever-growing hazardous materials industry with addressing each question are presented are considered. 2 through 11. in Tables

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U.S. Governmentwork not protectedby US. copyright.

Table 1 "ENT/SCIENTIFIC QUESTIONS FREQUENTLY OF HAZARDOUS MATERIALS ADDRESSED AT SPILLS

. may be intakes
. aquatic

dangerous

if

it

enters

water

toxicity: 10-100 ppm/96 h r / % / (Species not specified] food chain concentration potential: none Pentachlorophenol (3,5) 1 . What was spilled? a . Health hazards 2 . How hazardous are the spilled substances? dust 3. What precautions should be taken to irritating to eyes, nose and throat protect human health and welfare? if inhaled, will cause coughing or 4. Where will the spilled substances go? difficult breathing 5. can the spilled substances be contained dangerous to breathe at the spill site? corrosive to skin 6 . What containment and cleanup strategies can solid be used to minimize human health effects poisonous if swallowed and environmental damage? will burn skin and eyes 7. What are the environmental and sociocauses smarting of the skin and first economic resources at risk from the degree burns on short exposure; may spilled substances? cause secondary burns on long exposure 8. h i h a t are the environmental and sociodust or vapor irritates skin and mucous economic protection priorities? membranes, causing coughing and sneezing. 9. What were the impacts of the spilled ingestion causes loss of appetite, substances on humans and the environment? respiratory difficulties, anesthesia, 10. What was the fate of the spilled sweating, coma. Overexposure can substances? cause death. b . Water pollution 3. THE PENTACHLOROPHENOLSPILL AND harmful to aquatic life in very low ASSOCIATED PROBLEMS concentrations may be dangerous if it enters water On July22, 1980, a collision occurred between intakes the Panamanian bulk carrier Sea Daniel and aquatic toxicity: 5ppm/3 hr/trout/lethal/ the German container ship Testbank in the fresh water Mississippi River Gulf Outlet, a ship channel food chain concentration potential: approximately twenty miles southeast of New 30-100 = "bioaccumulation factox" Orleans, Louisiana. As a result of the damage lethal concentration = 100-300 mg/l (ppb) to the ships, four containers were lost overEPA Criterion (fresh water) = 6.2 ppb/24 board. The four containers held household hr averagehot to exceed 14 ppb ever goods, lube oil, scrap metal, and twelve tons EPA acceptable limit food in = 2 mg/ of pentachlorophenol (PCP) in 50 pound paper person/day bags. In addition, an unknown number of dnnns of hydrobromic acid ( I i b r ) were lost overboard When the PCP spill first occurred, initial or ruptured, spilling hydrobromic acid onto attention was focused on the hydrobromic acid the decks of the Testbank and into the water. which was emitting a poisonous vapor cloud and The containers of lube oil, household goods, of the Mississippi River mixing with the waters and scrap metal posed no unusual problems for Gulf Outlet, causing immediate problems for the cleanup crews and were subsequently removed divers, other response personnel, and nearby and disposed of. Response personnel were, townspeople. Fortunately, only small amounts however, immediately confronted with a were spilled and it was cleaned up and moved significant spill of hazardous materials with off the spill site within a matter of days the following characteristics: without major mishap. However, the pentachlorophenol presented a longer-term problem. Hydrobromic Acid ( 3 ) The PCP, in granular form, and resembling coarse a . Health hazards sand, disappeared into the bottom muds of the vapor ship channel where visibility is close to zero. poisonous if inhaled irritating to eyes, nose, and throat PCP isa biocide used as an insecticide, fungiliquid n cide, herbicide, algicide, disinfectant, i and poisonous if swallowed antifouling paints, but marketed primarily as will burn skin and eyes a wood preservative (12). Health effects from will cause frostbite skin and lung the P a itself range from minor inhalation causes severe irritation of irritation to death.AS a technical grade nose and upper respiratory tract, lung to 92% chemical, the product contained 88% only injury. Ingestion causes burns of mouth pentachlorophenol. The remainder of the product and stomach. Contact with eyes causes of impuriwas comprised of an unknown mixture severe irritation and bums. Contact ties ( 8 ) . Through high resolution gas chrcmatowith skin causes irritation and burns. graphy (GC) and high resolution gas chromatob. Water pollution graphy-mass spectrometry (GC-KS) analyses of dangerous to aquatic life in high PCP the original cargo, was it revealed that the concentrations

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was composed of three major compounds (pentachlorophenol, tetrachlorophenol, trichlorophenol), ten minor chlorinated organic chemicals (pentrachlorobenzene, hexachlorobenzene, dioctyl phthalate, hexachlorodiphenyl ether, heptachlorodiphenyl ether, octachlorodiphenyl ether, hexachlorodibenzofuran, dexachlorodibenzo-p-dioxin, heptachlorodibenzo-p-dioxin, octachlorcdibenzop-dioxin), and trace amounts of two hundred chlorocarbons (7)

Table 2 Potential Problems Associated with Answering Managementhcientific Question: (1) WHAT WAS SPILLED?

. unwillingness/inability .
. -

Although the dioxins were present in only small amounts, their extraordinarily high toxicity and high bioaccumulation tendencies make them potentially very dangerous to both humans and the environment (4,ll). Therefore, besides the problems created by the spill of hydrobromic acid and pentachlorophenol i n t o the Mississippi River Gulf Outlet, there were many additional health and environmental difficulties caused by the discovery of dioxins in the spilled cargo.
. S . Coast Guard and For the next month, Uthe response groups from other federal, state, and private sources continued the very difficult task of trying to clean the bottom of the ship channel and surrounding areasa pollutant of which was now essentially invisible. The effort cost nearly three million dollars, the evacuation of over 75 people, the closure of 400 square miles of Louisiana waterways to fishing, considerable anxiety over the impact to the health of local residents and response personnel, and public loss of confidence in 4 ) . Fortunately, there the local fishery ( were neither any reports of significant illness or injury as a result of the incident, or long-term contamination problems in any of delayed the fish or shellfish from the region.

. .

of spiller to disclose complete identity of spilled product placarding/labeling too general incorrect, incomplete, missing or destroyed cargo manifest missspelling of trade, common, or technical name of product presence of potentially hazardous impurities in product spilled potential risk to field, laboratory, and response personnel when working unknown with substances Table 3 Potential Problems Associated with Answering Management/Scientific Question: ( 2 ) HOW HAZARDOUS ARE THE SPILLED SUBSTANCES?

. possibility

The problems resulting from spills such as the PCP incident of hazardous materials are, however, complex and dangerous. These problems must be anticipated before incidents occur and should be included in the development of the response decision-making process. Some of the most common problems associated with hazardous materials spills are listed in Tables 2 through 11. For the purposes of pre-spill planning, they have been divided and placed under the most into groups appropriate spill question.

. . .

.
. . .

for following hazardous materials combinations: to be spilled singly in or explosives gases flammable and combustible liquids flammable solids oxidizers and organic peroxides poisons radioactive materials corrosives potential for the following health effects (singly or in combination) from: Immediate fires pathogenx organisms corrosives explosions irritants poisoning bioaccumulation contamination suffocation mutagens chemical burns carcinogens intense heat teratogens extreme cold poisons available information on hazards of spilled products sparse or incorrect. impurities more toxic than product aquatic and marine pollution information not available or incomplete for many substances many highly dangerous substances odorless, colorless, tasteless dangerous reactivity with water, air, light, sediment incompatibility of spilled substances with dangerous or unknown reactions among spilled substances synergystic effectsof spilled substances on humans and environment criteria for federal and state "acceptable" based on levels of conteminant be can insufficient data.

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Table 4 Potential Problems Associated with Answering Management/Scientific Question: (3) WHAT PRECAUTIONS SHOULD BE TAKEN M PROTECT "AN HEALTH AND WELEA ' R E ?

. unknown or .

. personnel risks at spills of unknown substances . unwillingness of some response personnel adhere to established safety guidelines
. response

.
to

. .

. . . . .

. . .

. . .
.
.

. .

personnel unfamiliar or untrained in use of personal protection equipment proper protective equipment and clothing may not be available lack of pre-spill planning by all or part of response comunity confusion about chain of command among disaster response groups evacuation may be physically impssible or impractical evaluation of protective measures difficult in "mystery" spills response efforts hampered by severe or unusual weather unknown atmospheric dispersion rates for many hazardous substances traffic control often difficult unnecessary anxiety and panic caused by Table 6 irrespondible press extreme public or political pressure to Potential Problems Associated with "do something" before response personnel Answering Management/Scientific Question: safely prepared (5) CAN TEiE SPILLED SUBSTANCES BE SITE? CONTAINED AT SPILL Table 5 state of the art for hazardous materials Potential Problems Associated with containment and cleanup not sufficient for Answering Management/Scientific Question: safe and easy handling of some commonly (4) WILL THE SPILLED SUBSTANCES GO? spilled substances danger of explosion, fire, or other unknown or unpredictable physical/chemical immediate hazard behavior of one or more of the spilled insufficient containment equipment, substances or reaction products in water, personnel, and materials sediment, and air public and political pressure to do so environmental pathways and processes involved before response personnel ready in uptake and transfer of contaminants rapid loss of product to surrounding waters, poorly understood in many cases sediment, or air difficult to track the spread of some sublimited visibility in vicinity of spill site stances due to lack of color or odor, inclement weather sinking, mixing with sediment, water, and air strong winds and water currents occurrence o f spills into complicated water systems such as estuaries, channels, canals, Table 7 marshes, lagoons, bayous, rivers, etc. data on weather patterns and/or water Potential Problems Associated with circulation (including tidal and estuarine Answering Management/Scientific Question: of flow) insufficient for prediction (6) W H A T CONTAINMENT AND STRATEGIES accurate spill trajectories CAN BE USED TO MINIMIZE HUMAN HEALTH EFFECTS physical and chemical characteristics of AND ENVIRONMENTAL DAMAGE? water in area not hediately available (e.g., pH, salinity, temperatures, oxygen state of the art cleanup and containment content) techniques and equipment not sufficient stratification and mixing rates and patterns for safe and easy handling of some commonly known for local waters not always spilled substances alteratjon of noma1 water and atmospheric federal ands t a t e response agencies still flow patterns due unusual or severe weather fate, learning about hazardous materials conditions effects, cleanup strategies, etc. rapid atmospheric dispersion of product cleanup techniques sometimes more damaging to environment than spilled substance

.
.

. . .

unpredictable physical/chemical behavior of one or more of the spilled substances or reaction products in water, sediment, and air environmental pathways and processes involved in uptake and transfer of contaminants poorly understood in many cases difficult to track the spread of subsome stances due to lack of color or odor, sinking, mixing with sediment, water, and air Occurrence of spills into complicated water systems such as estuaries, channels, canals, marshes, lagoons, bayous, rivers, etc. data on weather patterns and/or water circulation (including tidal and estuarine flow) insufficient for prediction of accurate spill trajectories physical and chemical characteristics of water in area not immediately available oxygen (e.g., pH, salinity, temperatures, content) stratification and mixing rates and patterns not always known for local waters alteration of normal water and atmospheric flow patterns due unusual or severe weather conditions rapid atmospheric dispersion of product

= R E

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. presence of large nunhers of personnel, equipment, and activities sometimes

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.
.

. .

statistical and logistics problems in sampling large numbers of individuals from varied socioeconomic groups damaging to environment unnecessary public anxiety and worry caused local resource information not always by sensational press coverage and irresponavailable for area sible statements by responding officials local weather may prevent use of most documentation of contamination of impacted effective cleanup techniques ground water surface water, soil, air, locating acceptable and safe disposal sites well water for cleanup materials and spilled product Environmental often difficult lack of faunal and floral surveys - prespill of impacted environments Table 8 Of lack of data on background levels ambient contaminants Potential Problems Associated with confusion of impact with natural variability Answering Management/Scientific Question: of population (7) WHAT ARE THE RESOURCES AT RISK FROM THE difficulty in finding dead organisms for SPILLED SUBSTAXCES?. body counts especially, in remote areas and with small sized organisms fate and effects of some spilled substances designing damage assessment program acceptthroughout the environment unknown or poorly able to all parties understood determining what quantity of contaminant data on socioeconomic and environmental caused impact resources of area may often by unavailable preventing press from causing panic in or limited, especially early in the spill consumer markets of threatened resources may be difficult to predict accurate formulation and acceptance of sampling plan trajectories for the spilled substances may not be possible to confirm existing Table 11 published resource data for area local sensitivities and priorities may be Potential Problems Associated with unknown or poorly understood Answering Management/Scientific Question: (101 WHATWAS THE FATE OFTHE SPILLED Table 9 SUBSTANCES?

Potential Problems Associated with Answering Management/Scientific Question: ( 8 ) WHAT ARE THE ENVIRONMENTAL AND SOCIOECONOMIC PROTECTION PRIORJ.TIES?

. data on socioeconomic and environmental resources of area often unavailable . fate and effects of spilled substances often unknown or not understood . habitats or organisms mandated by law to be protected sometimes overlooked . political and public pressure occasionally

. .

force protection of inappropriate resources at expense of others local input and data on resources sometimes overlooked or ignored local priorities sometimes Overlooked or ignored Table 10

Potential Problems Associated with Answering Management/Scientific Question: (9) V R I A T ARE T H E IMPACTS OF THE SPILLED SUBSTANCES ON H U M A N S AND THE ENVIRONMENT? Human Health and Welfare lack of prespill medical data on effected individuals and populations influences of normal background contaminants on impacted individuals and populations lack of epidemiological information on impacted subjects legal difficulties in attempting to sample civilians

unknown physical/chemical behavior of spilled products in environment inability to follow spread of spilled substances throughout the environment by direct observation of lack of information on conversion spilled substances to breakdown products, reaction products, metabolic products in the environment ignorance of pathways, receptors, processes involved in an interaction between the substances and the living and non-living environment difficulties in quantifying amounts of spilled substance: recovered in cleanup operation evaporated carried away by air or water currents converted to other products absorbed adsorbed taken up by living organisms dissolved dissipated throughout the environment
4.
IMPLICATIONS OF HAZARWUS MATERIAIS

. .
.

SPIUS The human appetite for advancement and convenience has created unlimited opportunities for industry and the economy, but infinite problems for both human health and welfare and the environment. The present products and by-

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products of modern technology increasingly have crosby, D.C. Memorandum to Captain Richard to cause an appalling variety of the capability Clements, USCG On-Scene Coordinator, injuries, contamination, diseases, or deaths. summarizing interpretations of PCP spill Furthermore, it is no longer possible to avoid with recommendations for future action; contamination during normal contact with air, August 11, 1980. water, food, ground, and materials. It is not necessary to belabor the environmental message Department of Transportation. Hazardous of global pollution but it and implications Materials 1980 Emergency Response Guidebook. should be stated that the role of hazardous U.S. Department of Transportation, materials in the pollution issue is, indeed, Publication No. DOT P 5800.2. significant Laseter, J. L. and DeLeOn,I. R. The PentaWhile spills may be only one source of chemical chlorophenol (PCP) Spill in the Mississippi pollution, the spills factor is easier to (MRGO): Chemistry River Gulf Outlet document and control than many other types of Support. Final Report. Center for pollution. It is unfortunate that the manufacBio-Organic Studies, University of ture, transportation and use of hazardous New Orleans, New Orleans, Louisiana. so rapidly and that most materials is increasing marine spills of oil and hazardous substances Lindsay, D. R. Letter to William Ernst, occur in rivers, ports, and harbors, and, NOAA Scientific Support Coordinator, therefore, near major metropolitan areas (131, October 9, 1980. but it is encouraging that it may still be possible to have a positive impact on the Maynard, N. G. Research Required for Prediction problem. As the incidence of hazardous materials of Oil Spill Effects. Presented in the dump site problems, spills, and contamination First Greek/U.S. Working Conference on grows, public awareness has also increased Oceanography Related to Environmental considerable. Superfund legislation has been Problem, Aegina, Greece, July 7-11, 1980. passed by the Senate. Federal, state and private response groups are improving their Maynard, N. G. Techniques for the Optimization abilities to respond safely and effectively Tested at of Scientific Spill Response and better cleanup and containment techniques the Burmah Agate Oil Spill. Conference and materials are being developed rapidly. 9 8 1 h-ctic Marine Proceedings of the 1 Disposal sites are being selected with more care Oilspill Program(AMOP), June 16-18, 1981, and planning, while the reconnaissance and Edmonton, Alberta. sites continues. Ultimately, cleanup of old perhaps, more stress will be placed on preven- Nillson, C., Norstrom, A., Anderson, K., tion of the accidents and situations which cause Rappe, C . Impurities in Commercial spills. Through these influences, it is hoped Products related to pentachlorophenol. of the hazardous materials that at least some In: Faof K. R. (ea.) Pentachlorophenol: spill problems can be eliminated or ameliorated. Chemistry, Pharmacology, and Environmental Toxicology. New York, Plenum Press. 5 . REPERENCES . The New Orleans PentachloroThompson, M. A Braithwaite, K. W . Pollution from Hazardous phenol Spill: The Federal, State and Substances: The Legislative Response. to the Spill and the Local Response Proceedings of the Conference on Oil and of the Consequences and Implications Hazardous Materials Spills: PrevenfionSpill. Unpublished Report to the National Control-Cleanup-Recovery-Disposal; Oceanic and Atmospheric Administration, December 3-5 , 1979, pp. 1-3. Boulder, Colorado, 24 pp.

Buckley, J. L. and Wiener, S. A. Hazardous Materials Spills: A Documentation and Analysis of Historical Data. Environmental Protection Technology Series, U.S. EPA EPA-600/2-78-066, April, 1978. Chris. Chemical Hazards Response Information U.S. System. Department of Transportation, Coast Guard, Camandant Instruction 9 7 8 . M16465.12, October, 1 Clements, Captain Richard. Final Federal On-Scene Coordinator Report M/V on: Sea Daniel/M/V Testbank Pentachlorophenol Discharge Near Shell Beach, Louisiana, July 22, 1 9 8 0 .

U.S.

Coast Guard. Polluting Incidents in and around U.S. Waters. Calendar Year 1978 and 1979. Department of Transportation, USCG, COHDTINST Ml6450.2 (Old CG-487).
Control of

Wilder, I. and Lafornara.

Hazardous Material Spills i n the Water Environment. Water and Sewage Works, 119, 1 (821, January, 1982.

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