Upload
lakeisha-campbell
View
201
Download
0
Embed Size (px)
Citation preview
69
Oceanography and Marine Biology: An Annual Review,
2005,
43
, 69-122 © R. N. Gibson, R. J. A. Atkinson, and J. D. M. Gordon, Editors
Taylor & Francis
BIOLOGICAL EFFECTS OF UNBURNT COAL IN THE MARINE ENVIRONMENT
MICHAEL J. AHRENS
1
& DONALD J. MORRISEY
2
National Institute of Water and Atmospheric Research Ltd,
1
PO Box 11-115, Gate 10, Silverdale Road, Hamilton, New Zealand
2
PO Box 893, 217 Akersten Street, Nelson, New Zealand
E-mail: [email protected], [email protected]
Abstract
Unburnt coal is a widespread and sometimes very abundant contaminant in marineenvironments. It derives from natural weathering of coal strata and from anthropogenic sourcesincluding the processing of mined coal, disposal of mining wastes, erosion of stockpiles by windand water, and spillage at loading and unloading facilities in ports. Coal is a heterogeneous materialand varies widely in texture and content of water, carbon, organic compounds and mineral impu-rities. Among its constituents are such potential toxicants as polycyclic aromatic hydrocarbons(PAHs) and trace metals/metalloids. When present in marine environments in sufficient quantities,coal will have physical effects on organisms similar to those of other suspended or depositedsediments. These include abrasion, smothering, alteration of sediment texture and stability, reducedavailability of light, and clogging of respiratory and feeding organs. Such effects are relatively welldocumented. Toxic effects of contaminants in coal are much less evident, highly dependent on coalcomposition, and in many situations their bioavailability appears to be low. Nevertheless, thepresence of contaminants at high concentrations in some coal leachates and the demonstration ofbiological uptake of coal-derived contaminants in a small number of studies suggest that this maynot always be the case, a situation that might be expected from coal’s heterogeneous chemicalcomposition. There are surprisingly few studies in the marine environment focusing on toxic effectsof contaminants of coal at the organism, population or assemblage levels, but the limited evidenceindicating bioavailability under certain circumstances suggests that more detailed studies would bejustified.
Introduction
Coal is one of the oldest and most widespread anthropogenic contaminants in marine and estuarineenvironments. This review addresses the question of whether unburnt coal represents an environ-mental risk. The review arose from a request to assess the potential ecological effects associatedwith proposed storage and shipping of coal from an existing port. Coal is a heterogeneous materialand different forms vary in their physical and chemical properties. In the course of this study, itwas found that there was considerable information on the chemical composition and physicalproperties of coal, as might be expected for a major industrial feedstock. While some commoncomponents of coal, such as polycyclic aromatic hydrocarbons (PAHs) and trace metals mightbecome environmental contaminants and have the potential to cause adverse biological effects atsufficiently high concentrations, it was surprising that there was relatively little information on thebioavailability of contaminants from coal, or on biological effects at the levels of organisms,
MICHAEL J. AHRENS & DONALD J. MORRISEY
70
populations or assemblages directly related to coal, either in the laboratory or field. This lack ofinformation on the ecological effects of unburnt coal was unexpected in view of the commonoccurrence of coal in the marine environment and the continuing importance of coal as a sourceof heat and as an industrial feedstock.
Coal has been traded by sea at least since Roman times. Its co-occurrence with iron ore in theEnglish Midlands was one of the factors that made possible the large-scale production of iron andlaid the foundations for the industrial revolution of the late 18th–19th centuries. From then untilthe 1960s coal was the world’s single most important source of primary power. In the late 1960sthis role was taken by oil, but the imbalance is likely to swing back again because of the relativesizes of remaining reserves of coal and oil (equivalent to 200 yr and 40 yr for coal and oil,respectively, at current rates of production; World Coal Institute 2004). The current global politicalclimate is also encouraging oil-importing countries to reduce their reliance on oil and become moreself-sufficient in energy production and reserves of coal are much more widespread geographicallythan those of oil.
Global coal production and consumption
In 2002, total global production of hard coal (bituminous and anthracite — the different types ofcoal are described below) was 3837 million tonnes (Mt) and that of brown coal/lignite 877 Mt(these and other economics data were taken from the Web sites of the World Coal Institute 2004,Coalportal 2004 and Australian Coal Association 2004). In contrast to oil-exporting countries, majorproducers of hard coal have a wide geographical distribution, as shown in Table 1, although thequality (rank) of coal varies greatly. Production of brown coal is dominated by Germany, Greeceand North Korea but, because of its lower economic value and relatively high water content, it isusually consumed close to the point at which it is mined. Transport of coal by sea (includinginternational trade) is dominated by hard coals, and bituminous types in particular. The latter are
Table 1
Production and export of hard coal in
2002 by country
CountryTotal production, Mt (%)
Exports, Mt
Thermal Coking
PR China 1326.0 (34.6) 72.0 13.8U.S. 916.7 (23.9) 16.2 18.3India 333.7 (8.7) 0 0Australia 276.0 (7.2) 91.3 107.5South Africa 223.0 (5.8) 67.7 0.9Russia 163.6 (4.3) 36.1 9.0Poland 102.6 (2.7) 19.1 3.5Indonesia 101.2 (2.6) 65.6 7.4Ukraine 82.9 (2.2) n.d. n.d.Kazakhstan 70.6 (1.8) n.d. n.d.Canada 67.9 (1.8) 3.4 23.4Colombia 39.4 (1.0) 34.4 0
Total 3837 435.0 195.4
Data from World Coal Institute 2004 and Coalportal 2004,values for exports are estimates. Percentages based on totalworld production.
UNBURNT COAL IN THE MARINE ENVIRONMENT
71
used for electricity generation (‘thermal’ coal) and for industrial processes, particularly the man-ufacture of steel (‘coking’ coal). Anthracite is the least abundant of the world’s coal stocks andconsequently represents only a very small part of world trade in coal, despite its high energeticand economic value.
Just over 60% of current coal consumption is used to produce heat and power, including about39% of global electricity generation. A further 16% is used in the steel industry, in blast furnacesfuelled by coal and coke. Domestic uses and non-metallurgical industries (including the manufactureof cement) each represent about 5% of total consumption. Many of the world’s largest economiesrely on coal to generate 50% or more of their electricity, including the United States (50%), Germany(52%) and, significantly, the emerging economies of China (76%) and India (78%). Between 1995and 2020, world energy demand is predicted to rise by 65% and fossil fuels are expected to meet95% of this increase. Much of the coal used in power generation, however, is of low rank (ligniteand sub-bituminous types) and its relatively low economic value and high water content make itunattractive for international trade. Consequently, more than 60% of the coal used for electricitygeneration globally is consumed within 50 km of its source.
Roughly 14% (630.4 Mt) of world production of hard coal is currently traded internationally,69% for power generation and 31% for metallurgical use. This compares with a trade of 427.4 Mtin 1994, an increase of 47.5% over the last decade. Australia is the world’s largest exporter of hardcoal with 21% (91.3 Mt) of thermal and 55% (107.5 Mt) of coking coal sent to more than 35countries, principally Japan (90.2 Mt) and other Asian countries (Republic of Korea 25.3 Mt, Taiwan17.2 Mt, other Asian nations 11.0 Mt), but also Europe (31.8 Mt), India (13.6 Mt), north Africa, theMiddle East and South America. Other important exporters of thermal coal are China, Indonesia,South Africa, Russia, Colombia, Poland and the U.S., whereas Canada, in addition to these countries,also exports coking coal. Exports of both categories are expected to rise in the near future, withAustralia increasing exports of coking coal and all exporting countries increasing their exports ofthermal coal. The major coal importing countries are Japan (estimated 91.8 Mt in 2002), theRepublic of Korea (44.4 Mt), Taiwan (42.6 Mt), Germany (31.6 Mt), the United Kingdom (22.5 Mt)and other European Union states (153.8 Mt).
These figures illustrate several relevant points. First, the amount of coal traded by sea is huge,even in an era that we commonly think of as being dominated, in terms of energy production, byoil and gas. Second, the exporters and importers of hard coal are often separated by large distances,for example Australia and Europe. Third, the centres of production and consumption of coal, andthe shipping routes connecting them, continue to shift as the centres of industrial production andpower consumption change. In particular, the rising industrial outputs of China and India are likelyto bring continuing changes to global trade in coal. China’s exports and imports of hard coal havetripled over the last decade while India’s imports have more than doubled.
Coal forms the backbone of heavy industry and electricity generation in many countries. Toensure an uninterrupted supply, utilities and industrial facilities that need to run continuously oftenstockpile coal for 30–90 days of consumption (Davis & Boegly 1981a). For example, it is estimatedthat approximately 100 Mt of coal are stockpiled in the U.S. alone (data for 1997 cited by Cook &Fritz 2002). For logistical reasons, coal stockpiles are commonly located close to waterways andtherefore represent a major source of coal particulates and leachates to the aquatic environment.
The need for information on ecological effects of coal in the marine environment
The need to assess the effects of unburnt coal in the marine environment may arise from newsources of contamination or from remobilisation of coal already present and incorporated intosediments. Development of new coal mines and associated coal washing facilities (or the continuedoperation of existing mines) near the coast brings the possibility of environmental contamination,
MICHAEL J. AHRENS & DONALD J. MORRISEY
72
and requires assessments of environmental risk. Coal storage and loading facilities at ports are alsopotential sites of contamination, often on a very large scale. For example, the world’s largest exportcoal handling facility at the Port of Newcastle, New South Wales, Australia, has storage area for3.5 Mt of coal (Australian Coal Association 2004). Coal travels from trains or storage areas toships via conveyors and in very large volumes. The Port of Hay Point in Queensland, Australia,for example, can load in excess of 20,000 t h
–1
(R. Brunner, Ports Corporation of Queensland,personal communication). During the transfer, storage and loading operations there is potential forloss of coal to the surrounding environment through spillage and wind and water erosion. Manycoal-handling ports operate best-management practices to reduce these fugitive losses, but anassessment of the appropriate level of reduction requires an understanding of the mechanisms ofcoal’s environmental effects. Measures that are adequate to prevent unacceptable reduction in waterclarity, for example, might not be considered adequate if exposure to coal had a demonstrablyadverse toxic effect on aquatic organisms.
In the past, control of contamination by particulate coal around mines and ports was less strictthan it is today and sediments in these areas are likely to contain a substantial legacy of historicalcoal contamination. Capital dredging may remove these sediments, resuspending some of the coalinto the water column and transferring the remainder to spoil disposal areas (Birch et al. 1997).Changes to patterns of water movement, for example following deepening of navigation channelsto accommodate vessels of larger draught or infilling of intertidal areas for port or other develop-ments, could also lead to erosion and remobilisation of coal-bearing sediments (French 1998).Again, assessment of the associated environmental risks requires understanding of the mechanismsof effect.
Scope of the review
The present review focuses on the ecological effects of unburnt coal in the marine environment.The effects of products of combustion of coal, such as fly ash, which have been reviewed elsewhere(e.g., Duedall et al. 1985a,b, Swaine & Goodarzi 1995), and the by-products of coking and coalgasification are not considered. Also excluded are effects of materials that may be added to coal toimprove its handling characteristics during transport and storage, such as glycol or chlorinatedwater used to create slurries for transfer by pipeline, and potential hazards from ‘synfuels’ (com-binations of coal with oil emulsions, used for power generation, coking and steel manufacture insome countries). Effects of spoil from coal mines, including acid mine drainage, are also outsidethe present scope because, again, they have been extensively reviewed elsewhere (e.g., Evangelou1995, Geller et al. 2002) and because their effects derive not just from the presence of coal butalso (perhaps mainly) from associated rocks and minerals (although coal-pile leachates may begenerally similar in quality to acid mine drainage: Davis & Boegly 1981a). While the focus of thisreview is the marine environment, information on the quality and ecotoxicology of stockpileleachates is also considered. Although leachates are generally derived from freshwater (rainfall orwater sprayed to suppress dust) they provide a potential conduit for coal-related contaminants toenter the marine environment. Also included are studies of physical effects of coal on freshwaterorganisms, since the mechanisms of effect are likely to be the same in saline waters. The Discussionattempts to evaluate and synthesise the information from the perspective of environmental riskassessment and mitigation. Although this approach may deviate from a typical scientific review, a‘risk assessment’ format may be useful for those faced with assessing and managing effects of coalin the marine environment.
The review begins with an overview of coal types, because there are differences among themin their potential ecotoxicological effects. Sources and the distribution of coal in the marineenvironment are then discussed. Consideration of effects of coal on marine organisms begins with
UNBURNT COAL IN THE MARINE ENVIRONMENT
73
physical effects such as smothering and abrasion. Next, chemical information on coal is reviewedin relation to its role as a potential source of contaminants to the marine environment. Followingthis, the rather limited range of information on effects of coal-derived contaminants at the biologicallevels of the cell, organism, population and assemblage is described. This description focusesspecifically on coal-derived contaminants, rather than reviewing the general literature on effects ofthe contaminants concerned. The Discussion addresses the question of whether unburnt coal pre-sents a problem in the marine environment, identifying scenarios (such as chemical environmentalconditions and type of coal) for which it is or is not likely to pose an ecological hazard, and othersfor which we have insufficient knowledge to make an assessment. Finally, management options formitigating potential environmental effects and directions for future research are briefly considered.
Where possible, published, widely accessible sources of information have been used and the‘grey literature’ avoided. However, the paucity of information on many aspects of coal’s environ-mental effects has made some reference to grey literature unavoidable. For up-to-date backgroundinformation on current production and trade in coal, reference is made to relevant sources on theInternet, many of which are provided by bodies representing the coal industry.
Types of coal
Variation in age and conditions of formation gives rise to a range of types of coal, classified intofour broad categories (‘ranks’). These vary in their chemical composition (and, therefore, theirpotential for biological effects), their energy content and, ultimately, their use. Alternative systemsof coal classification are summarised by Ward 1984. Lignite (‘brown coal’) is the least mature rankand contains relatively little carbon and energy, and a relatively large proportion of water andvolatile matter. It represents about 20% of world reserves of coal and is mainly used for powergeneration. The second type of low-rank coal, sub-bituminous, has a higher carbon content(71–77%), lower water content (10–20%) and is used for power generation, production of cement,and various industrial processes. It ranges in appearance from dull and dark brown to shiny andblack, and in texture from soft and crumbly to hard and strong. It represents about 28% of worldcoal reserves. Of the ‘hard’ coals, the less organically mature form, bituminous coal, is used forpower generation (‘thermal’ or ‘steam’ coal) and manufacture of iron and steel (‘coking’ coal). Itrepresents 51% of world coal reserves. Bituminous coal varies in content of volatile matter, whereasthe most organically mature and highest ranked coal, anthracite, always contains less than 10%volatile matter and is capable of burning without smoke. It is hard, has a high carbon content (ca90%) and has various domestic and industrial uses. Although it is the most valuable form of coal,it constitutes only 1% of world coal reserves.
Other important determinants of coal quality, and its corresponding utility, relate to its mineralcontent. For example, sulphur, chlorine and phosphorus occur in substantial amounts in some coalsand have the potential to generate corrosive acids upon oxidation or heating. Other coals may havehigh contents of metals and metalloids. These chemical properties not only affect the behaviour ofa specific type of coal in its intended use, but also significantly determine its behaviour in theenvironment.
Sources and distribution of particulate coal in the marine environment
Coal enters the marine environment through a variety of mechanisms (Figure 1), including naturalerosion of coal-bearing strata (Shaw & Wiggs 1980, Barrick et al. 1984, Barrick & Prahl 1987).Papers by Short et al. (1999), Boehm et al. (2001), Mudge (2002) and Van Kooten et al. (2002)feature a debate about the source of background hydrocarbon contamination in the Gulf of Alaska,
MICHAEL J. AHRENS & DONALD J. MORRISEY
74
with one group suggesting oil-based sources and the other suggesting coal. Mudge (2002) concludedfrom a multivariate statistical assessment of the relative contributions of coal, oil seeps, shales andrivers that the hydrocarbons probably derived from a mixture of sources, whose contributions variedacross the sampling area.
Anthropogenic inputs of coal occur at several stages of the coal utilisation sequence (Figure 1).These include: disposal of colliery waste into intertidal or offshore areas (Eagle et al. 1979, Santschiet al. 1984, Norton 1985, Limpenny et al. 1992, McManus 1998); wind and water erosion of coastalstockpiles (Sydor & Stortz 1980, Zhang et al. 1995); coal-washing operations (Pautzke 1937,Williams & Harcup 1974); spillage from loading facilities (Sydor & Stortz 1980, Biggs et al. 1984);‘cargo washing’ (the cleaning of ships’ holds and decks after offloading dry bulk cargoes by washingwith water and discharging over the side; Reid & Meadows 1999); and the sinking of coal-poweredand coal-transporting vessels (French 1993a, Chapman et al. 1996a, Ferrini & Flood 2001).
As a result of these various inputs, unburnt coal occurs very commonly in marine sediments(Goldberg et al. 1977, 1978, Griffin & Goldberg 1979, Tripp et al. 1981) and may represent aconsiderable proportion of the sediment. The abundance of coal in the marine environment is likelyto be greatest adjacent to storage and loading facilities in coal producing and importing countries,around spoil grounds receiving colliery waste, along shipping lanes and in areas receiving terrestrialrunoff from catchments where coal mining occurs (French 1993b, Allen 1987). In sediments offthe northeast coast of England, for example, subject to inputs of coal from natural weathering anddumping of colliery waste, coal represented up to 27% of combustible matter by dry weight (Hyslopet al. 1997).
Coal can be a common contaminant even away from such point sources and over larger spatialscales. Goldberg et al. (1977) found that coal, coke and charcoal together represented up to 1.9%by dry weight of the surficial sediments in Narragansett Bay, Rhode Island, U.S., mostly consistingof particles <38
µ
m. The bay has a large human population and intense industrial activity. Theangular shape of the coal particles suggested that they had been introduced directly to the coastalenvironment, rather than being transported via rivers. Goldberg et al. suggested that this materialwas derived from coal-burning ships or coal burning on adjacent land. Similar results were found
Figure 1
Sources of coal to the marine environment.
Unburnt and fugitive
airborne emissions
Dumping of tailings
and colliery waste
Slumping & runoff
from storage areas
Natural erosion
of coal seams
Loading operations
Accidental releases
Transport &
cargo washing
Preparation
& washing
UNBURNT COAL IN THE MARINE ENVIRONMENT
75
for Chesapeake Bay (Goldberg et al. 1978), where likely sources included coal mining in theadjacent catchment of the Susquehanna River, in addition to coal-burning ships and domestic andindustrial uses on the adjacent land. Goldberg et al. (1978) noted that the local power companyformerly dredged the lower parts of the river, separated the coal, and used it for power generation.This practice stopped once dams were constructed on the lower river, trapping coal and othersediments until they were periodically resuspended and flushed out of the dams by storms. Anextreme example of the wide geographical extent of human inputs of coal to the marine environmentis provided by the presence of coal clinker at depths of 3000–5000 m in the Venezuelan Basin inthe Atlantic (Briggs et al. 1996).
Geographical patterns of input and distribution of coal in the marine environment vary at arange of scales. Long-term, historical changes include shifts in centres of coal production, such asthe rise and fall of British coal output in the 19th and 20th centuries and the more recent rise incoal production in China. Accompanying these are changes in trading routes for coal. For example,in 1982, the seaborne trade in thermal coal was 61 Mt in the Atlantic and 25 Mt in the Pacific,with respective values for coking coal of 48 and 73 Mt. By 2002, following average annual growthin seaborne trade of 8% for thermal coal and 1.8% for coking coal, the equivalent figures were170 and 233 Mt for thermal coal and 60 and 114 Mt for coking coal (World Coal Institute 2004).In addition to these long-term changes in sources of coal contamination, concentrations at aparticular location may also show short-term changes related to factors such as seasonal variationin fluvial discharge (French 1993c).
In addition to direct inputs to estuarine and coastal environments, coal may be transported fromits source (natural or anthropogenic) by rivers. This process may introduce a variable lag betweenproduction and contamination, depending on the distance involved and the storage capacity of theriver system (Allen 1987). Man-made
alterations to patterns of river flow, such as dams, mayincrease this lag. Hainly et al. (1995) estimated that the three dams on the Susquehanna River,which flows into the Chesapeake Bay, had accumulated about 250 Mt of sediment, of which about20 Mt (8%) was coal. Remobilisation of this stored coal (and other contaminants), for examplewhen the dams reach the end of their functional lives, may provide a significant source of contam-ination to downstream environments. Similarly, contaminated estuarine or coastal sediments mayact as a source of future contamination through remobilisation. French (1993a, 1998) suggestedthat new inputs of coal to the Severn Estuary (United Kingdom) must derive from erosion ofcontaminated sediments already in the estuary because production of coal in the nearby Welshcoalfields had effectively stopped by the time of his study. Estimates indicated that mudflats andsaltmarshes in the estuary contained 10
5
–10
6
t of coal (Allen 1987, French 1998). As rising sealevels bring about increased rates of erosion of intertidal flats and saltmarshes in many parts of theworld (e.g., Adam 2002, Scavia et al. 2002), remobilisation of historic contaminants, includingcoal, may become increasingly important.
Because coal generally has a lower specific gravity than many other components of sediments(the specific gravity of coal varies with its ash content, ranging from 1.2–2.9 g cm
–3
; Alpern 1977,compared with 2.65 g cm
–3
for quartz; Brady & Weill 2002), transport by water movement mayresult in larger particles of coal being transported and deposited with smaller, denser particles ofsands and gravels. Settling times and, therefore, transport distances will also be greater for a givenparticle size. In intertidal sediments of the Severn Estuary, coal particles (silt to sand size) weremost abundant in the finest-textured sediments (Allen 1987).
Physical effects of coal on marine organisms
Most of the mechanisms whereby particulate coal may exert a physical effect on organisms areshared with other types of suspended and deposited sediments and have been reviewed elsewhere.
MICHAEL J. AHRENS & DONALD J. MORRISEY
76
For example, Moore (1977) reviewed the effects of particulate, inorganic suspensions on marineanimals and Airoldi (2003) reviewed the effects of sedimentation on biological assemblages ofrocky shores. These effects are therefore only dealt with briefly here. Moore (1977) made thedistinction, from the perspective of biological effects, between scouring by larger particles, suchas sands, and the turbidity-creating effects of smaller particles, such as silts and clays. Many animalsand plants living on rocky shores trap sediments and, thereby, influence rates of sediment transport,deposition and accretion (Airoldi 2003), and this is equally true for animals living in soft sedimenthabitats (e.g., Wolanski 1995, Young & Harvey 1996, Esselink et al. 1998, Norkko et al. 2001).The reviews by Moore (1977) and Airoldi (2003) show that, conversely, sediments affect theabundance and composition of marine organisms and assemblages when in suspension and follow-ing deposition. Effects may be lethal or sublethal and may act directly (e.g., by abrasion, scour orsmothering) or indirectly (e.g., by alteration of the nature of the substratum or by modification ofprocesses of predation or competition). Airoldi (2003), however, pointed out that the mechanismsby which sedimentation affects marine organisms are often poorly understood and that differentaspects of sediment transport, such as burial, scour and turbidity, are often confounded and notexplicitly differentiated in studies.
Direct effects
Increased concentrations of suspended particulate coal in the water column may cause abrasion ofanimals and plants living on the surface of the sea bed or on structures such as rocks or wharf piles(Emerson & Zedler 1978, Kendrick 1991, Hyslop et al. 1997 and see references in Moore 1977and Airoldi 2003). The probability and severity of this effect will depend on the concentration, sizeand angularity of the coal particles and on the strength of water currents (Newcombe & MacDonald1991, Lake & Hinch 1999). Newcombe & MacDonald (1991) pointed out that the particle dose towhich an organism is exposed (a function of the concentration of suspended material and theduration of exposure) is a more relevant measure of stress than concentration alone but that durationis often not reported in studies of the effects of suspended sediments. Mean suspended solidsconcentrations of 1000–3000 mg l
–1
have been recorded in coal pile runoff in Canada, exceedingCanadian water quality criteria (10 mg l
–1
) by three orders of magnitude (Table 4, p. 84: Fendingeret al. 1989, Curran et al. 2000). Because of its generally lower specific gravity, larger particles ofcoal will be transported further by a given current speed than particles of quartz sand, potentiallyproducing greater abrasion. Hyslop & Davies (1998) tested the hypothesis that reduction in occur-rence and biomass of the green alga
Ulva lactuca
on shores receiving inputs of colliery waste wasdue to physical scouring. Laboratory tests compared the effects of three size categories of waste(<0.5 mm, 0.5–2.0 mm and >2.0 mm) under still and turbulent conditions. Over 8 days, plantsgained weight when no colliery waste was present but lost weight in the presence of waste. Maximalweight loss occurred in the presence of waste of grain size 0.5–2.0 mm (vs. <0.5 mm and 0–2.0 mm)under turbulent conditions, suggesting that the coarse sediment acted as an abrasive and may havebeen responsible for the removal of components of the ephemeral algal flora of shores receivingcolliery waste in northeast England. In contrast to the effect on macroalgae, the distribution ofanimals on the same shores was not affected by the presence of the waste (Hyslop et al. 1997).
Particles of coal in suspension will also reduce the amount and possibly the spectral quality(Davies-Colley & Smith 2001) of light that reaches the sea bed or other underwater surfaces, in amanner similar to other suspended particles (Moore 1977). This, in turn, may affect growth ofplants such as seaweeds, seagrasses, and microalgae on the surfaces of sediments and rocks (e.g.,Duarte 1991, Preen et al. 1995, Vermaat et al. 1996, Terrados et al. 1998, Longstaff & Dennison1999, Moore et al. 1997). Again, the magnitude of this effect will depend on the amount and size
UNBURNT COAL IN THE MARINE ENVIRONMENT
77
of coal particles in suspension (which will, in turn, depend on rate of supply and patterns of watermovement), duration of exposure and existing water clarity (Newcombe & MacDonald 1991).
Deposition of coal dust on the surface of plants above and below water may also reducephotosynthetic performance. Mangroves growing around South Africa’s largest coal-exporting port,Richards Bay, accumulate deposits of coal dust on both upper and lower leaf surfaces and onbranches and trunks (Naidoo & Chirkoot 2004). The presence of the dust reduced photosynthesis,measured as carbon dioxide exchange and chlorophyll fluorescence, by 17–39%. There was noevidence that coal particles were toxic to the leaves, but mangroves closest to the source of thedust appeared to be in poorer health than those further away. The amount of dust accumulated onleaves varied among mangrove species, with
Avicennia marina
, which has relatively hairy leaves,accumulating more than
Bruguiera gymnorrhiza
or
Rhizophora mucronata
.Suspended particles in general may clog feeding and respiratory organs of a wide range of
marine animals, reducing efficiency of feeding and respiration and possibly damaging the organs(see reviews by Newcombe & MacDonald 1991, Newcombe & Jensen 1996, Wilber & Clarke2001), or, as in the case of some bivalve molluscs, cause reduction in the rate or efficiency offeeding or cause it to cease altogether (see discussions in Moore 1977, Bayne & Hawkins 1992).Moore (1977) provided a taxonomic review of information on the effects of suspended sedimentson animals. Groups generally intolerant of higher levels of suspended sediments include sponges,some scleractinian corals, serpulid polychaetes, bivalve molluscs and ascidians, but there is con-siderable variation in tolerance within each group. It is reasonable to assume that coal will havesimilar effects across the same range of taxa, but this has not been determined.
In a study of the effects of coal on ventilation and oxygen consumption in the Dungeness crab(
Cancer magister
), there was no measurable effect over an exposure period of 21 days relative tocrabs living in clean water (Hillaby 1981). In this experiment, however, the coal was mixed intothe sand in the bottom of the aquaria, and was not kept in suspension, so the response to suspendedmaterial may not have been measured. Furthermore, coal-amended sediments were allowed toequilibrate for at least 15 days in flow-through tanks prior to beginning the experiments, whichmay have allowed fine particles of coal to be flushed out of the sediment. The lack of significantdifferences in oxygen consumption between treatments was, in part, due to large within-treatmentvariability because variance within treatments increased with exposure duration and proportion of coalto sand. A previous study (Pearce & McBride 1977, cited by Hillaby 1981), in which some coalremained in suspension throughout the duration of the experiment, reported that particles of coalprogressively accumulated in the crabs’ gills. This accumulation may have affected respiration andoxygen uptake although these were not measured in the experiment.
In a freshwater study involving an early example of
in situ
toxicity testing, Pautzke (1937)exposed young trout (
Oncorhynchus
mykiss
gairdneri
(cited as
Salmo gairdneri
) and
Oncorhynchusclarkii
(cited as
Salmo clarkii
)) to suspended coal washings (a mixture of crushed coal andassociated quartz, slate and other impurities) by confining them in mesh cages in a contaminatedstream. He reported 100% mortality among
O. mykiss
after 2.5 h and among
O. clarkii
after 0.5 h.There was no mortality among fish of either species exposed to the same mine water without thewashings (neither exposure nor control treatments were replicated). The concentration of suspendedmaterial in the contaminated stream was not explicitly stated (a figure of 3 oz gallon
–1
[22.5 g l
–1
]was given but it is unclear whether this was in the test area of the stream or closer to the washingarea). The dead fishes showed heavy secretions of mucus from the skin and gills, to which particlesof coal adhered. Coal and slate particles were also found in the stomachs. Pautzke also noted a‘haemorrhagic appearance’ to the heart and liver. In a later study, suspended particles of coal of200 mg l
–1
were reported to reduce growth rate in
O. mykiss
, but did not kill them (Herbert &Richards 1963, cited in Gerhart et al. 1981).
MICHAEL J. AHRENS & DONALD J. MORRISEY
78
Suspended sediments can also cause mortality of eggs and larvae of fishes and benthic inver-tebrates (Auld & Schubel 1978, Wilber & Clarke 2001). Eggs, larvae and, in some species, adultfishes exhibit rapid increases in adverse effects as the duration of exposure to suspended sedimentsincreases, implying the existence of a threshold concentration resulting in adverse effects (Newcombe& Jensen 1996). However, it should be noted that these studies did not specifically assess effectsof suspended coal, so extrapolations must be made with caution.
As coal settles out of suspension onto the sea bed, its most direct effect is likely to be smotheringof animals and plants. Around wharves where coal is loaded and unloaded the accumulation ofspilled coal may be considerable. French (1998) found a horizon of coarse coal debris 10 cm thickin the sedimentary record at Lydney Harbour on the Severn Estuary (United Kingdom), representingspillage from a former coal wharf. Examples of the effects of rapid deposition of sediment onbenthic macrofaunal assemblages have been reported for soft sediments (McKnight 1969, Peterson1985, Fahey & Coker 1992, Smith & Witman 1999) and rocky intertidal areas (Daly & Mathieson1977, Littler et al. 1983). Several of these studies reported high levels of mortality among the animalsaffected and many reported that species distributions in affected areas were related to the degreeof sediment deposition (reviewed by Airoldi 2003). Circumstantial evidence also indicates thatadverse effects of sediments can be due to inhibition of larval settlement and recruitment (Airoldi2003). In the case of soft-sediment benthos, mortality is likely to be greater when the depositedsediment is different to that naturally present at the site (Maurer et al. 1986). Because of coal’soften relatively low density, larger particles of coal may be deposited with smaller, denser particlesof sands and gravels (Barnes & Frid 1999) and effects on benthic organisms may be correspondinglylarge.
Rocky shores affected by sediments are mainly occupied by four groups of organisms withdifferent life-history traits: (1) long-lived, sediment-tolerant species; (2) opportunistic species ableto recolonise rapidly following mortality resulting from burial and scour; (3) species that migrateinto and out of the affected area as the degree of burial changes; and (4) species that trap sedimentsand are able to tolerate burial and scour. Characteristics that appear to confer the ability to tolerateburial and scour include the regrowth of upright portions from surviving basal structure; opportu-nistic cycles of reproduction and growth or vegetative reproductive capability; apical meristemsthat enable growing parts to remain above the sediment surface; tough, wiry bodies or thalli; erectmorphology that reduces the settlement of sediment; physiological characteristics that confertolerance of darkness, anoxic or hypoxic conditions and high concentrations of sulphides (Airoldi2003). Similarly, on soft-sediment shores, experimental studies show that some species of seagrassrespond to moderate rates and depths of sediment burial by increasing the shoot internodal andleaf-sheath length, rate of development of new leaves and vertical growth (Marbà & Duarte 1994,Duarte et al. 1997). Field studies of seagrass assemblages along gradients of siltation found thatspecies richness and biomass declined rapidly when the silt and clay content of the sedimentexceeded a threshold (Terrados et al. 1998, Bach et al. 1998). It may be assumed that depositionof large amounts of fine coal particulates will elicit similar effects.
Indirect effects
Deposition of coal on the sea bed will cause changes in the physical environment, particularly thecharacter of the substratum, and give rise to indirect effects on benthic organisms. These mayinclude infilling of rocky crevices that act as important habitats for benthic organisms such as crabsand lobsters (Shelton 1973) and reduced sediment stability due to the relatively high erodibility ofcoal particles, making the sediment less suitable for animals to live in. Moore’s (1977) taxonomicreview of effects of sediment deposition on soft-sediment benthos includes such indirect effectscaused by alteration of habitat. Conversely, in naturally homogeneous sediments, such as fine muds,
UNBURNT COAL IN THE MARINE ENVIRONMENT
79
the presence of coarser particles of coal may increase the heterogeneity of the sediment, allowinga larger range of animals to inhabit it. The previously mentioned coal clinker found at depths of3000–5000 m in the Venezuelan Basin in the Atlantic, for example, provided a hard substratum forcolonisation by an often-abundant, suspension-feeding anemone,
Monactis vestita
(Briggs et al.1996). Accumulations of coal particles on sandstone ridges off the Mediterranean coast of Israelenhanced the otherwise limited availability of hard substrata (Siboni et al. 2004). Particles werecolonised by barnacles, bryozoans and serpulid polychaetes and grazed by a variety of gastropods.A potential extension of this effect is provision of substrata for recruitment and establishment ofsubstratum-specific, non-indigenous species (Carlton 1996), particularly in ports where coal isloaded and unloaded and where international shipping provides a vector for the introduction ofexotic species (Carlton 1985).
Indirect physical effects may also be biologically mediated (see discussion by Chapman 2004).Reduction in growth and abundance of plants as a result of reduced water clarity with consequenteffects on primary consumers, inhibition of recruitment or removal of adult competitors, predatorsor grazers, selection of tolerant species and a host of other factors may give rise to a range ofindirect physical effects of the presence of suspended and deposited sediment in the marineenvironment (reviewed by Moore 1977 and Airoldi 2003). Reduced water clarity can also reducethe feeding efficiency of visual predators such as fishes (see Wilber & Clarke 2001 for a recentreview). Equivalent effects due the presence of coal are presumably likely, but no examples werefound in the literature.
Chemical properties of coal
From a chemical standpoint, coal is a heterogeneous mixture of carbon and organic compounds,with a certain amount of inorganic material in the form of moisture and mineral impurities (Ward1984). In addition to its predominant elemental building block, carbon, coal contains a multitudeof inorganic constituents that may greatly affect its behaviour in, and interactions with, the envi-ronment. Unburnt coal can be a significant source of acidity, salinity, trace metals, hydrocarbons,chemical oxygen demand and, potentially, macronutrients to aquatic environments (Tables 2–6),which pose potential hazards to aquatic organisms (Cheam et al. 2000). Trace metals and polycyclicaromatic hydrocarbons (PAHs) are present in amounts and combinations that vary with the typeof coal (Tables 2 and 3). For a detailed review of trace metal content of coals, the comprehensivemonograph by Swaine (1990) is recommended. A fraction of these compounds may be leachedfrom coal upon contact with water, such as during open storage or after spillage into the aquaticenvironment (Figure 2). Whether or not these can be leached from the coal matrix and affect aquaticorganisms will depend on the type of coal, its mineral impurities and environmental conditions,which together determine how desorbable these potential contaminants are. For example, leachingof metals and acids strongly depends on coal composition, particle size and storage conditions andis accelerated in the presence of oxygen or oxidising agents and if coal remains wet betweenleaching events (Davis & Boegly 1981a,b, Querol et al. 1996).
Acid-generating potential
One of the most common environmental problems in the handling of many coals is the generationof acid leachates. Rainwater runoff from coal piles can be highly acidic due to the oxidation ofpyrite impurities to sulphuric acid, leading to pH values as low as pH 2 (Table 4, Scullion &Edwards 1980, Davis & Boegly 1981b, Fendinger et al. 1989, Carlson & Carlson 1994). The acidityof coal leachates is primarily a function of a coal’s sulphur content, such that highly pyritic coals(sulphur content >3%) generally have low pH values of around 2, whereas sulphur-poor coals
MICHAEL J. AHRENS & DONALD J. MORRISEY
80
Tabl
e 2
Inor
gani
c ch
emic
al p
rope
rtie
s of
par
ticul
ate
coal
; co
ncen
trat
ions
by
dry
wei
ght
Units
British coals
Germancoals
Canadiancoals
Spanish coals
Eastern U.S.coals
Midwest U.S.coals
Western U.S.coals
New South Wales and Queensland
SW China
South Island coals*
North Island coals*
ANZECC ISQG-lowANZECC ISQG-high
Ori
gin
U.K
.G
erm
any
Can
ada
Spai
nU
.S.
U.S
.U
.S.
Aus
tral
iaC
hina
New
Zea
land
New
Z
eala
ndR
ank
BL
,BB
SB,
BB
BSB
SB,
BA
SB,
BSB
, B
N%
1–2
0.9–
1.4
1.2–
1.4
S%
0.5–
42.
2–9.
52.
0–5.
21.
14.
60.
5–3.
0C
l%
0.01
–10.
14–0
.25
0.00
3–0.
116
0.01
61.
060.
06–0
.33
Ag
ppm
0.01
–0.0
60.
02–0
.08
0.01
–0.0
7<
0.2–
10.
003–
0.11
0.01
2–0.
191
3.7
As
ppm
1–73
1.5–
500.
2–24
05.
3–35
.71.
8–10
01.
0–12
00.
34–9
.8<
1–55
5–35
,000
<1.
5–27
.5<
2.25
2070
Bpp
m0.
5–16
02–
236
9–36
014
1–43
65–
120
12–2
3016
–140
1.5–
300
10–3
4247
–708
Ba
ppm
<6–
500
45–3
5010
–100
036
–91
72–4
205.
0–75
016
0–16
00<
40–1
000
8.3–
148
21–8
1C
dpp
m0.
02–5
0.02
–21
0.26
–0.3
30.
10–0
.60
0.1–
650.
10–0
.60
0.05
–0.2
<0.
3–0.
9<
0.7–
1.7
1.5
10C
opp
m0.
4–60
7–30
0.2–
214–
12.5
1.5–
332.
0–34
0.6–
7.0
<0.
6–30
<0.
1–14
.00.
4–6.
8C
rpp
m1–
454–
802.
1–95
11–3
810
–90
4.0–
602.
4–20
<1.
5–30
0.4–
20.9
0.6–
14.1
8037
0C
upp
m5–
240
10–6
00.
2–52
7–16
5.1–
305–
443.
1–23
2.5–
400.
95–9
.41.
0–13
.665
270
Fpp
m5–
500
20–3
7031
–890
50–1
5029
–140
19–1
4015
–500
Fepp
m10
4–33
,265
1780
14,9
0018
00–7
7,50
0G
app
m3–
105–
102.
9–11
0.8–
100.
8–6.
51–
200.
14–3
.00.
2–5.
8
81
UNBURNT COAL IN THE MARINE ENVIRONMENT
Ge
ppm
2–80
1.2–
20.
10–6
.01–
430.
1–3.
0<
0.3–
300.
07–7
.80.
05–0
.5H
gpp
m0.
03–2
.00.
1–1.
40.
02–1
.30.
05–0
.47
0.03
–1.6
0.02
–6.3
0.02
6–0.
400.
26–2
90.
12–0
.56
0.19
–0.2
40.
151
Mn
ppm
1–16
0055
, 68
2–60
040
–86
2.4–
616–
210
1.4–
220
2.5–
900
1.3–
2.8
7–63
Mo
ppm
0.1–
206–
300.
4–13
0.6–
320.
10–2
20.
3–29
0.10
–30
<0.
3–6
<0.
02–0
.42
0.12
–0.7
6N
ipp
m3–
6015
–95
2–38
8–33
6.3–
287.
6–68
1.5–
180.
8–70
0.6–
27.5
2.9–
11.0
2152
Ppp
m<
10–1
000
40–1
240
45–5
200
68–2
7515
–150
010
–340
10–5
1030
–400
0<
1.6–
29.3
<2.
2–9.
4Pb
ppm
1–90
00.
1–39
01.
8–53
5–21
1.0–
180.
8–22
00.
7–9
1.5–
600.
3–18
.01.
3–16
.050
220
Sbpp
m1–
100.
14–5
.00.
1–16
0.7–
3.2
1.7–
210
<0.
04–3
.7<
0.05
–0.2
92
25Se
ppm
0.3–
5.1
0.6–
5.5
<0.
1–8.
00.
5–1.
61.
1–8.
10.
4–7.
70.
4–2.
70.
21–2
.5Sn
ppm
0.3–
753.
6, 3
.92–
150.
9–2.
30.
2–8.
00.
2–51
0.1–
15<
0.9–
150.
14–7
.50.
52–1
7.5
Th
ppm
0.7–
6.7
1.6–
4.4
0.1–
92–
6T
lpp
m0.
6–1.
70.
01–0
.72
0.20
–0.3
91.
8–9.
00.
71–5
10.
62–5
.7<
0.2–
8<
0.00
4–6.
7<
0.00
5U
ppm
1.1–
3.0
0.3–
2.2
0.4–
120.
9–26
0.40
–2.9
0.31
–4.6
0.3–
2.5
0.4–
5V
ppm
3–15
031
–179
3.4–
200
14–7
614
–73
11–9
04.
8–43
4–90
0.68
–13.
81.
3–18
.5Z
npp
m3–
7000
14–1
742
2.0–
6235
–95
2–12
010
–530
00.
3–17
12–7
30.
7–27
.51.
0–55
.520
041
0
Ref
eren
ce1
and
22
2 3
4 in
5 a
nd 6
4 in
5 a
nd 7
4 in
5 a
nd 7
8 in
59
10,
11 a
nd 1
211
and
12
1313
Abb
revi
atio
ns: E
mpt
y ce
lls =
not
ana
lyse
d; I
SQG
= in
teri
m s
edim
ent q
ualit
y gu
idel
ine,
L =
lign
ite, S
B =
sub-
bitu
min
ous,
B =
bitu
min
ous,
A =
ant
hrac
ite, *
= c
once
ntra
tions
cal
cula
ted
from
ori
gina
l da
ta (
ash)
by
mul
tiply
ing
by a
sh f
ract
ion
Ref
eren
ces:
1 F
ranc
is 1
961,
2 S
wai
ne &
Goo
darz
i 19
95,
3 Q
uero
l et
al
1996
, 4
Glu
skot
er e
t al.
1977
, 5
War
d 19
84,
6 Fe
ndin
ger
et a
l. 19
89,
7 D
avis
& B
oegl
y 19
81b,
8 S
wai
ne19
77,
9 D
ing
et a
l 20
01,
10 S
olid
Ene
rgy,
New
Zea
land
Ltd
. 20
02,
11 S
oong
& B
erro
w 1
979,
12
Sim
197
7, 1
3 A
NZ
EC
C 2
000
MICHAEL J. AHRENS & DONALD J. MORRISEY
82
Tabl
e 3
Org
anic
che
mic
al p
rope
rtie
s of
par
ticul
ate
coal
; al
l co
ncen
trat
ions
in
ppm
(=
µ
g g
–1
) dr
y w
eigh
t
Nam
eR
ank
Tota
l al
ipha
tics
Tota
l ar
omat
ics
Tota
lPA
Hs
AN
TN
AP
PHE
BaP
BaA
BbF
CH
RFL
FLT
PYR
Ref
eren
ce
‘U.S
. co
al’
B67
0–96
020
0–21
601
W W
ashi
ngto
n co
alL
, SB
, B
, A0.
2–33
50
a
2
Coa
l or
cok
e pa
rtic
leB
1.43
2.74
4.94
1.27
1.46
1.32
1.53
1.53
1.62
1.65
3Pe
nnsy
lvan
ia a
nd
Mar
ylan
d co
als
B3.
4–29
.917
.6–6
2.4
0.34
–0.6
50.
08–0
.46
0.25
–1.1
70.
12–0
.36
0.04
–0.4
14
Vir
gini
a co
al10
81.8
2.57
13.
268
26.8
030.
535
1.97
86.
281
15.3
32
b
7.21
89.
190
7.05
15
AN
ZE
CC
& N
OA
A
ISQ
G –
Low
= E
RL
40.
085
0.16
0.24
0.43
0.38
40.
60.
665
6, 7
AN
ZE
CC
& N
OA
A
ISQ
G –
Hig
h =
ER
M45
1.1
2.1
1.5
1.6
2.8
5.1
2.6
6, 7
MO
EE
LE
L0.
560.
370.
340.
750.
49pe
rs.
com
mun
.
Abb
revi
atio
ns: Q
uota
tion
mar
ks =
geo
grap
hica
l ori
gin
not s
peci
fied
; em
pty
cells
= n
ot a
naly
sed;
a
= to
tal n
-alk
anes
in
µ
g g
–1
of o
rgan
ic c
arbo
n;
b
= s
um o
f chr
ysen
e an
d tr
iphe
nyle
ne;
L =
lig
nite
; SB
= s
ub-b
itum
inou
s; B
= b
itum
inou
s; A
= a
nthr
acite
; E
RL
= e
ffec
ts r
ange
low
; E
RM
= e
ffec
ts r
ange
mea
n; I
SQG
= i
nter
im s
edim
ent
qual
ity g
uide
line;
LE
L =
low
est
effe
cts
leve
l; A
NT
= a
nthr
acen
e, N
AP
= n
apht
hale
ne;
PHE
= p
hena
nthr
ene;
BaP
= b
enzo
(a)p
yren
e; B
aA =
ben
z(a)
anth
race
ne;
BbF
= b
enzo
(b)fl
uora
nthe
ne;
CH
R =
chry
sene
; FL
= fl
uore
ne; F
LT =
fluo
rant
hene
; PY
R =
pyr
ene;
AN
ZE
CC
= A
ustr
alia
n an
d N
ew Z
eala
nd G
uide
lines
for
Fre
sh a
nd M
arin
e W
ater
Qua
lity;
NO
AA
= N
OA
A S
cree
ning
Qui
ck R
efer
ence
Tab
le f
or O
rgan
ics;
MO
EE
= M
inis
try
of t
he E
nvir
onm
ent
and
Ene
rgy
guid
elin
e (O
ntar
io,
Can
ada)
for
par
ticul
ate
boun
d PA
H,
as p
erso
nal
com
unic
atio
n K
imIr
vine
(16
Jun
e 20
04).
Ref
eren
ces:
1 T
ripp
et a
l. 19
81,
2 B
arri
ck e
t al.
1984
, 3
Cha
pman
et a
l. 19
96a,
4 F
endi
nger
et a
l. 19
89,
5 B
ende
r et
al.
1987
, 6
AN
ZE
CC
200
0, 7
Buc
hman
199
9
UNBURNT COAL IN THE MARINE ENVIRONMENT
83
(sulphur content 1–2%) produce more pH neutral runoff (Davis & Boegly 1981b, Tiwary 2001,Cook & Fritz 2002). Higher sulphur content in coal also leads to higher suspended solids concen-trations in runoff due to the breakdown of the coal matrix during oxidation. Furthermore, longerleaching duration increases suspended solids concentrations by promoting microbial degradationof sulphur compounds (Stahl & Davis 1984). The strong acid-producing potential of coal pile runoffhas been confirmed in numerous studies of simulated or actual leaching of coal stockpiles (Hall &Burton 1982, Tease & Coler 1984, Swift 1985, Tan & Coler 1986, Carlson 1990, Cook & Fritz2002) and has been shown to exert negative effects on terrestrial vegetation (Carlson & Carlson1994), groundwater quality (Carlson 1990, Cook & Fritz 2002) and stream invertebrate communities(Swift 1985). Apart from sulphur content, a number of other factors are likely to influence coalleachate pH, including age and particle size of coal, rainfall frequency and amount, coal moisturecontent and the presence of sulphur-oxidising bacteria (Davis & Boegly 1981a). Conversely, acidityof coal pile leachates can be greatly diminished by promoting the growth of sulphate-reducingbacteria within coal piles (Kim et al. 1999). In the marine environment, significant impacts of acidicleachates are unlikely, due to the vast buffering capacity of seawater bicarbonate, except perhapsfor constricted and poorly flushed embayments and estuaries. Water quality guidelines such as
Figure 2
Factors affecting behaviour and effects of unburnt coal in the marine environment (COD = chemicaloxygen demand). Influential factors in boxed arrows.
AcidityNutrients
COD Radio-nuclides
Hydro-carbons
Tracemetals
Contam-inants
Turbidity AbrasionAlteredsedimentproperties
Weathering& handling
Pile configurationMineral contentParticle sizeErosive forcesDensity
pHRainfallRank
Sulphur contentMineral content
Particle sizeContact time
MicroorganismsTemperature
Oxygen
Chemical Effects Physical Effects
Biota
P450 inductionMetallothioneinsBioaccumulationMembrane destabilisation
Reduced growth, reproduction & abundance; elevated toxicity &mortality; altered population & community structure
DilutionBufferingPrecipitationComplexationSpeciationBioavailability
DilutionDistanceCurrentsFrequency
Leachates Particulates
Diminished photosynthesisSediment destabilisationSmotheringClogging of gillsFeeding impairment
MICHAEL J. AHRENS & DONALD J. MORRISEY
84
Tabl
e 4
Phys
icoc
hem
ical
pro
pert
ies
of c
oal
leac
hate
s. I
norg
anic
s
Ty
pe
of
leac
hat
eC
oal
ty
pe
and
ori
gin
Su
lph
ur
% d
wC
on
di-
tio
nT
SS
m
g l
–1
TD
S
mg
l
–1
Fil
ter
po
re
µ
mp
HE
C
µ
S cm
–1
SO
4
m
g l
–1
Al
mg
l
–1
As
µ
g l
–1
Cd
µ
g l
–1
Cr
µ
g l
–1
Cu
µ
g l
–1
Fe
mg
l
–1
Hg
µ
g l
–1
Ni
µ
g l
–1
Pb
µ
g l
–1
Se
µ
g l
–1
Zn
µ
g l
–1
Ref
.
Coa
l le
acha
teB
E
U.S
.4.
6L
ab0.
452.
1–3.
818
7– 4320
213– 40
600.
18–5
5n.
a.6–
1470
n.a.
n.a.
n.a.
1
Coa
l le
acha
teSB W
U.S
.1.
1L
ab0.
454.
6– 8
.327
– 670
35–1
890.
16–4
9n.
a.<
0.10
n.a.
n.a.
n.a.
1
Stoc
kpile
ru
noff
n.a.
n.a.
Fiel
d C
anad
aU
nfilt
3.1–
4.6
122– 17
1610
0– 1640
n.a.
500– 25
001.
0–71
.020
0– 3100
2
Stoc
kpile
ru
noff
n.a.
1–3
Fiel
d U
.S.
8–23
00
(470
)
2500
–16
00
(790
0)
?2.
3–3.
1 (2
.79)
1800
–96
00
(516
0)
66–4
40(2
60)
5–.6
00
(170
)<
1<
5–11
(7)
430– 14
00
(860
)
240– 18
00
(940
)
<0.
2–2.
5 (0
.4)
740– 45
00
(259
0)
<1–
30
(6)
2300
–16
,000
(6
680)
3 in
4
Stoc
kpile
ru
noff
n.a.
>3
Fiel
d U
.S.
38– 25
00
(420
)
1200
–75
00
(315
0)
?2.
5–3.
1 (2
.65)
870– 55
00
(508
0)
22–6
0 (4
3.3)
6–46
(2
0)<
1–3
(2)
<5–
11 (
7)10
–460
(2
30)
62–4
80
(265
)3–
7 (4
)24
0–46
0 (330
)
<1–
1 (1
)11
00–
3700
(2
180)
3 in
4
Stoc
kpile
ru
noff
n.a.
n.a
Fiel
d C
anad
a21
88 ±
34
02U
nfilt
3.2
± 3
.41.
9 ±
1.5
24 ±
24
35 ±
28
15.5
±
14.4
50 ±
30
22 ±
18
280±
300
5
Stoc
kpile
ru
noff
Coa
l fr
om
11 p
ower
pl
ants
n.a
Fiel
d U
.S.
247– 44
,050
(1
2,60
0)
?2.
1–7.
813
3– 2192
0 (6
880)
0–15
.7
(2.7
4)16
00–
3400
(2
100)
0.06
–93
,000
(10,
800)
6–23
,000
(5
890)
6 in
4
Stoc
kpile
ru
noff
??
Fiel
d,
U.S
.93
30–
14,9
00(1
1,70
0)
?2.
2–5.
810
0–75
0(2
60)
100– 61
00
(169
0)
10– 52
50
(114
0)
2400
–26
,000
(5
900)
7 in
4
Stoc
kpile
ru
noff
??
Fiel
d C
anad
a46
00–
11,6
00
(650
0)
?2.
4–2.
9 (2
.7)
1100
–69
00
(410
0)
48–7
5 (6
2)15
0– 1000
(4
20)
8 in
4
Gro
und-
wat
er
unde
r co
al p
ile
E U
.S.
Sulp
hur–
rich
Fiel
d,
U.S
.>
10,0
00?
2.2
Up
to
8480
Up
to
22,2
00U
p to
11
00U
p to
95
609,
10
Sim
ulat
edru
noff
E.
U.S
.2–
5L
ab32
2– 3300
?1.
7–3.
233
00–
24,0
0011
Stoc
kpile
ru
noff
E U
.S.
2–5
Fiel
dU
.S.
?1.
9–2.
028
00–
19,0
0011
Coa
l le
acha
teSB U
.S.
‘Low
’L
ab
0.45
7.0–
7.7
15–3
5040
–120
<0.
2–0.
80.
2–0.
50.
1–0.
60.
0017
–0.
0025
<0.
50.
4–2.
112
Coa
l le
acha
teSB
& B
Sp
ain
2.2–
9.5
Lab
Cen
tri-
fuge
dn.
a.0–
1851
0–34
57–
520–
700
100– 21
001–
7900
100– 21
,000
0–6
1–18
010
0– 42,0
0013
85
UNBURNT COAL IN THE MARINE ENVIRONMENT
Coa
l le
acha
teW
U.S
.L
owL
ab
?0–
0.1
0.05
–0.
080–
0.1
0.10
–1.
80–
20.5
0–0.
300–
0.95
0.1–
1.9
14
Coa
l le
acha
teW
U.S
.L
owL
ab
pH 7
.3?
Adj
ust.
to 7
.30.
5– 2.35
0–0.
180.
01–
0.95
0.7–
4.2
1.6–
7.9
0.4–
1.9
2.4–
3.5
0.7–
4.2
14
Coa
l le
acha
teW
U.S
.L
owL
ab
pH 4
.8?
Adj
ust t
o 4.
81.
76–
6.08
0.02
–0.
570–
0.22
0.9–
3.5
2.9– 21
.10–
0.5
1–0–
1.2
0–5.
014
Coa
l le
acha
teW
U.S
.N
o. 2
Low
Lab
?7.
48–
8.30
0.05
–0.
950.
1–0.
70.
09–
0.27
1.50
–6.
270.
06–
0.51
0–6.
00–
0.41
0–2.
11–
13.5
14
Coa
l le
acha
teE
U.S
.H
igh
Lab
?3.
08–
3.90
0–1.
92.
30–
4.79
0.43
–1.
956.
44–
63.9
0.29
–0.
4218
0– 323
0.01
–0.
220–
2.2
65–2
2014
Coa
l le
acha
teM
W U
.S.
0.6
Lab
?5.
9459
80.
3215
Coa
l le
acha
teM
W U
.S.
2.9
Lab
?2.
2233
,766
15,7
0015
Stoc
kpile
ru
noff
E U
.S.
2.7–
4.1
Fiel
dU
.S.
1.3– 17
.00.
002–
6.49
?1.
4–3.
110
50–
20,0
0079
6– 13,6
2519
.9–
1872
<1– 16
,240
954– 83
,536
25–<
100
3820
–19
,435
016
Gui
delin
es
CW
QG
(F
W)
FW
6.0–
9.0
SW
7.0–
8.7
0.00
5–0.
15.
0FW
0.
017
SW 0
.12
FW
1.0–
8.9*
SW
1.5–
56*
2–4
0.3
0.1
25–1
501–
71
3017
AN
ZE
CC
(F
W)
6–9
n.e.
n.e.
0.05
513
–24*
0.2
1.0
1.4
n.e.
0.6
113.
411
818
AN
ZE
CC
(S
W)
n.e.
n.e.
n.e.
n.e.
n.e.
5.5
4.4– 27
.4*
1.3
n.e.
0.4
704.
4n.
e.15
18
NO
AA
SQ
uiR
T
acut
e
n.e.
n.e.
n.e.
FW 0
.75
SW
n.e.
FW 3
40SW
69
FW 4
.3SW
42
FW
16–5
70*
SW 1
100–
10,3
00*
FW 1
3SW
4.8
n.e.
FW 1
.4SW
1.8
FW 4
70SW
74
FW 6
5SW
210
FW
13–1
86SW
290
FW 1
20SW
90
19
NO
AA
SQ
uiR
T
chro
nic
n.e.
n.e.
n.e.
FW 0
.087
SW n.e.
FW 1
50SW
36
FW 2
.2SW
9.3
FW
11–7
4*SW
50
FW 9
SW 3
.1FW
1SW n.
e.
FW 0
.77
SW 0
.94
FW 5
2SW
8.2
FW 2
.5SW
8.1
FW 5
SW 7
1FW
120
SW 8
119
Abb
revi
atio
ns:
n.e.
= n
ot e
stab
lishe
d; n
.a.
= n
ot a
naly
sed;
? =
no
info
rmat
ion
avai
labl
e; B
= b
itum
inou
s; S
B =
sub
–bitu
min
ous;
unfi
lt =
unfi
ltere
d;
±
= m
ean
±
sta
ndar
d de
viat
ion;
(pa
rent
hese
s) =
mea
n; T
SS =
tot
al s
uspe
nded
sol
ids;
TD
S =
tota
l di
ssol
ved
solid
s; E
= e
aste
rn;
W =
wes
tern
; M
W =
mid
wes
tern
; FW
= f
resh
wat
er;
SW =
sea
wat
er;
EC
= e
lect
rica
l co
nduc
tivity
; *
= t
rigg
er v
alue
dep
ends
on
spec
iatio
n of
ele
men
t; C
WG
Q =
Can
adia
n W
ater
Qua
lity
Gui
delin
e fo
rPr
otec
tion
of A
quat
ic L
ife;
AN
ZE
CC
= A
ustr
alia
n an
d N
ew Z
eala
nd G
uide
lines
for
Fre
sh a
nd M
arin
e W
ater
Qua
lity
(200
0);
trig
ger
leve
l fo
r pr
otec
tion
of 9
5% o
f sp
ecie
s; N
OA
A S
Qui
RT
= N
OA
A S
cree
ning
Qui
ck R
efer
ence
Tab
les
for
Inor
gani
cs i
n W
ater
; qu
otat
ion
mar
ks =
con
cent
ratio
n no
t sp
ecifi
ed.
Ref
eren
ces:
1 D
avis
& B
oegl
y 19
81b,
2 S
culli
on &
Edw
ards
198
0, 3
Cox
et a
l. 19
77,
4 D
avis
& B
oegl
y 19
81a,
5 C
urra
n et
al.
2000
, 6
Nic
hols
197
4, 7
And
erso
n &
You
ngst
rom
197
6, 8
Fea
ther
by &
Dod
d 19
77,
9 C
arls
on 1
990,
10
Car
lson
& C
arls
on 1
994,
11
Fend
inge
r et
al.
1989
, 12
Ger
hart
et a
l. 19
80,
13 Q
uero
l et
al.
1996
, 14
Cow
ard
et a
l. 19
78,
15 C
ook
& F
ritz
200
2, 1
6 Sw
ift
1985
, 17
Env
iron
men
t C
anad
a 20
02,
18 A
NZ
EC
C 2
000,
19
Buc
hman
199
9
MICHAEL J. AHRENS & DONALD J. MORRISEY
86
ANZECC (2000) recommend a general runoff pH to receiving waters (the guidelines do not specifywhether marine or freshwater) of between 6–9, primarily to minimise corrosion (presumably ofmetal equipment, though this is not stated). For preventing adverse biological effects, Perkins (1976)recommends that materials introduced into saltwater portions of coastal waters should not changereceiving water pH by more than
±
0.1 pH units from ambient conditions and at no time shouldthey alter pH beyond the range of 6.7–8.5. Notwithstanding, there are no published studies thatdocument drastic changes of seawater pH as a result of unburnt coal discharges.
Chemical oxygen demand
Coal pile leachates may have an increased chemical oxygen demand (COD) due to fine, suspendedcoal dust particles (Srivastava et al. 1994). Featherby & Dodd (1977) measured COD values of37–161 mg l
–1
in coal pile drainage, and it is likely that COD of unfiltered stockpile runoff mayexceed 1000 mg l
–1
when accompanied by elevated suspended solids concentrations.
Salinity
Coal pile runoff is often saline, due to salts formed during the oxidation and dissolution of mineralcomponents of coal (e.g., sulphate from pyrite oxidation). While coal-generated salinity may notbe important for the marine environment from a mass-loading perspective, the elemental compo-sition of coal pile runoff may differ from sea water. Total dissolved solids (TDS) concentrationsas high as 44 g l
–1
and electrical conductivity (EC) exceeding 8000
µ
S cm
–1
have been measuredin runoff of sulphur-rich coal piles (Nichols 1974, Carlson & Carlson 1994; see Table 4). Never-theless, on average, TDS concentrations of coal pile leachates do not exceed 15 g l
–1
(Table 4),which makes them less saline than typical sea water (ca 35 g l
–1
). Because of the naturally highsalinity and conductivity of sea water, the salinity inputs emanating from coal storage piles are notlikely to have significant ecological effects on marine organisms. However, coal pile salinity mayaffect terrestrial and freshwater biota before reaching the marine environment. For example, deathof terrestrial vegetation was observed at EC values above 4000
µ
S cm
–1
for soil solutions (Rendig &Taylor 1989).
Nutrients
There appear to be very few published data on the delivery of macronutrients into the aquaticenvironment from unburnt coal. Notwithstanding, coal does contain nitrogen and phosphorus inmeasurable quantities and a fraction of these nutrients appear to be leachable. Nitrogen makes upapproximately 1–2% (by weight) of mineral-free coal (Table 2) and is commonly associated withthe organic compounds present, because no nitrogen-bearing minerals are known in coals(Ward 1984). Gerhart et al. (1980) measured nitrate concentrations of 0.075–0.166 mg l
–1
and0.02–0.12 mg l
–1
in filtered leachates of low-sulphur, sub-bituminous coal (1.6% and 0.8% by weight,respectively), with a mean of approximately 0.07 mg l
–1
for the 0.8% coal leachates. Ammoniumnitrogen was approximately 0.15 mg l
–1
and dissolved organic nitrogen was 1.35 mg l
–1
. The greatlyelevated nitrate levels of some coal mine drainages are due to the use of explosives (Tiwary 2001).Oxidation of coal, combined with heating to 270°C, releases water-soluble organic nitrogen com-pounds such as phenanthridine, phenyl pyridine, pyrdine, and azaarenes such as quinoline andderivatives (Francis 1961, Barrick et al. 1984). Most nitrogen, however, is released only uponheating, either as ammonium or nitrogen oxides.
UNBURNT COAL IN THE MARINE ENVIRONMENT
87
Although phosphorus is an important element in living cells, its concentration in coal isgenerally low. Most coals contain between 10–2000 ppm phosphorus (Table 2; Francis 1961, Swaine1990, Rao & Walsh 1997), usually present as inorganic apatite, Ca
5
(PO4)
3
(F, OH), Ca
10
F
2
(PO
4
)
6
,or bound in aluminium hydroxides (Ward 2002), although some coals, such as Alaskan coal, containconcentrations up to 1% (Rao & Walsh 1997, 1999). Phosphorus content is often correlated withfluorine (Francis 1961), but there is disagreement whether P is typically associated with the organicor the mineral fraction. Gerhart et al. (1980) measured 0.02–0.12 mg l
–1
of total phosphorus infiltered leachates containing 0.8% sub-bituminous coal. This included between 0.01 and 0.1 mg l
–1
dissolved phosphorus and <0.001–0.008 mg l
–1
reactive phosphorus. Ward (2002) found up to 60%of the phosphorus in south Australian coals to be leachable by water washings, although he didnot report concentrations. Phosphorus showed variable distribution in these coal deposits, beingpresent in the water-exchangeable fraction in some coals but in the acid-soluble fractions in others.Querol et al. (1996), in a sequential leaching experiment, found between 88–94% of the phosphoruscontained in four Spanish coals (P content 68–200 ppm) to be leachable by nitric acid digestion,whereas little phosphorus was mobilised by water or ammonium acetate extractions of the samecoal samples. Other than the studies reported above, there are few published data describing howleachable phosphorus is under typical environmental conditions as encountered in stockpiles orwater-submerged coal.
Trace metals
As a decomposition product of ancient plants, coal contains virtually every element found in livingplant tissues, including trace metals (Table 2). Metals may be present as dissolved salts in porewaters, as metallo-organic compounds, or as mineral impurities (e.g., iron in pyrite, FeS, and zincin sphalerite, ZnS). Information on trace elements in coal has been reviewed comprehensively bySwaine (1990) and Swaine & Goodarzi (1995), including environmental aspects during mining andcombustion, though, unfortunately, not during storage and transport. Every type of coal contains asizable inorganic fraction, which affects its abrasive properties, stickiness, corrosion potential andrelease of trace metals (Ward 2002). The forms in which potentially toxic trace elements are heldin coal, and the extent to which these may be released, vary among coals and greatly depends onthe mineral matter present and, to a lesser extent, on coal rank. Many studies have indicated linksbetween the minerals present in coal and the concentration of particular trace elements (reviewedby Ward 2002). For example, As, Cd, Pb, Hg, Sb, Se, Tl and Zn are often associated with sulphidesand, therefore, show strong correlations with, for example, pyrite content of coal. Chromium anda number of other elements tend to associate with aluminosilicates, and strontium and barium areoften found in the presence of carbonates and aluminophosphate minerals. The low pH of sulphur-rich coal pile leachate favours dissolution of metals such as Fe, Cu, Mn, Cr and Zn (Anderson &Youngstrom 1976). Trace metal concentrations in runoff from stockpiles of sulphur-rich coal canbe so high as to endanger groundwater quality, in the absence of buffering capacity of the envi-ronment (Cook & Fritz 2002). For example, stormwater runoff from coal piles has been measuredto contain more than 100 mg l
–1
of aluminium and several mg l
–1
of copper, iron and zinc (Table 4).A study by Curran et al. (2000) of coal storage piles in Ontario, Canada, found total (i.e., dissolvedand suspended) metal concentrations to exceed Canadian water quality guidelines for Al, Cd, Cr,Cu, Fe, Pb and Zn (Table 4). While the metal loadings from stockpile runoff represented a relativelysmall input to the lake into which it drained, the authors suggested that there was potential forlocalised effects. Comparison of leachate metal concentrations with other international guidelineslisted in Table 4 shows that for virtually any metal, exceedances of the guideline values can befound for at least some coal samples.
MICHAEL J. AHRENS & DONALD J. MORRISEY
88
Although it has been stated that high concentrations of arsenic and selenium are typicallyassociated with coal-pile leachate (Cook & Fritz 2002), there is little evidence available in thepublished literature to support the contention that As and Se are especially elevated in leachates(Table 4). However, in areas with As-rich coal, such as southwest China (As content of up to 3.5%;Table 2, Ding et al. 2001), poisoning of humans (arsenosis) is a serious health concern, althoughthe toxicity derives primarily from contact with coal combustion products rather than from unburntcoal. Most coals contain 0.5–80 ppm As and 0.2–10 ppm Se (Swaine & Goodarzi 1995).
Coward et al. (1978) conducted elaborate leaching studies on coals from the western and easternU.S. to determine the dominant factors affecting leaching of metals (Table 4). In their factorialdesign, the investigators changed a number of variables believed to affect leachate quality in coalstorage piles, including pH, temperature, particle size, oxygen saturation, contact time and flow.While most variables showed some effect for some metals, raising the temperature and loweringthe pH generally increased leachate concentrations of most metals measured. Furthermore, sulphur-rich eastern coal had a much lower leachate pH than western coal and, on average, leachedconsiderably higher amounts of metals such as Cd, Co, Cu, Mn, Ni and Zn. Metal leaching fromwestern coals could be increased by lowering the pH of the leaching solution or adding complexingagents such as EDTA. The leachate data collected in Table 4 support the interim conclusion thathigh sulphur content and low leachate pH closely correlate with, and thus are useful indicators of,elevated metal concentrations in coal leachates.
The most comprehensive coal leaching study to date was conducted by Querol et al. (1996),who determined leachability of over 40 trace metals from four Spanish sub-bituminous to bitumi-nous coals by sequential extraction with water, ammonium-acetate and nitric acid (HNO
3
). Bymonitoring the release of trace metals and the distribution of the predominant mineral phases incoal (including different types of sulphides, sulphates, carbonates and aluminosilicates) after eachextraction step, Querol et al. were able to determine the likely mineral phases with which differentelements were associated. Elements associated with sulphides, sulphates and organic matter showedthe highest extraction efficiencies (up to 90% after HNO
3
treatment). These included As, B, Be,Mn, Mo, Ni, Pb, Se, Sr, Tl, U, V, Y, Zn and heavy rare-earth elements. In contrast, elements withstrong aluminosilicate affinity (e.g., Sn, Sb, Rb and Ta) had lowest leachability, and elements withintermediate affinity to aluminosilicates had intermediate mobility (Ba, Cd, Co, Cr, Cs, Cu, Ga,Ge, Li, Zr and light rare-earth elements). The major leachable fraction in coals was found in thenitric acid fraction, which mobilised the organic matter and sulphide-associated elements. However,all elements with strong organic and sulphide-sulphate affinities also had a water-leachable fraction,whose size depended on the degree of weathering of the coal sample. This study clearly showedthat mobility of trace elements in coal is controlled by their affinities to organic matter and mineralimpurities.
Metal toxicity to animals and plants is crucially dependent on the dissolved form, or speciation,of the metal, specifically the free metal ion concentration (Hall & Anderson 1995). Low pH valuesgenerally increase toxicity by increasing the free metal ion concentration (Gerhardt 1993, Wood2001). For example, increasingly acidic pH increases toxicity of Cd, Fe, Zn and Pb to many aquaticinvertebrates (Gerhardt 1993), and aluminium toxicity to plants occurs at soil pH below 4.5(Andersson 1988). For this reason, metal-rich and acidic coal leachates potentially represent acompounded stressor for aquatic organisms. In addition to uptake and associated toxicity fromdissolved metals, a certain fraction of metals may be accumulated from particles by ingestion (Wang& Fisher 1999) or direct contact.
In a study of effects of colliery waste dumped on the sea bed off the coast of northeast England,Hyslop et al. (1997) found that concentrations of metals in waste washed up on the beach weremuch lower than those in coal and waste prior to dumping (Table 6). Concentrations of Cr, Cu, Niand Pb in the washed-up coal were well below sediment quality guidelines for the protection of
UNBURNT COAL IN THE MARINE ENVIRONMENT
89
aquatic life. The fact that much of this metal content apparently leached out while the material wason the sea bed suggests that it might have been biologically available. Uptake of contaminantsderived from coal by sediment-living animals and plants raises the possibly that contaminants maybe transferred to higher levels of the food web and, if uptake is by mobile animals, exported toother areas (Wang 2002, Blackmore & Wang 2004).
Hydrocarbons
Unburnt coal contains a large fraction of volatile organic hydrocarbons, and organic compoundsfrom coal pile runoff include aliphatic and aromatic hydrocarbons (Tables 3 and 5; Barrick et al.1984, Stahl et al. 1984, Fendinger et al. 1989). In fact, the majority of the organic carbon in coalis believed to exist in the form of large, 5- or 6-membered rings of aromatic molecules (Neff 1979),and aromaticity increases with rank or coalification. Conversely, during the diagenetic coalificationprocess, the oxygen content of coals is lowered, which results in lower concentrations of hydroxy-lated aromatic compounds, such as phenols, which are most prevalent in lignitic coals (Schulz1997). Among the aromatic compounds, polycyclic aromatic hydrocarbons (PAHs) are of particularenvironmental interest, because they can be mutagenic or exert narcotic toxicity when present inbioavailable form. Studies of aquatic sediment contamination in the state of Washington (U.S.)have found high PAH concentrations within a few kilometres of industrial facilities or river systemsdraining coal-bearing strata (Barrick & Prahl 1987). However, it should be noted that chemicalalteration of coal, by refining or coking processes, tends to greatly concentrate PAHs (in additionto de novo synthesis at high temperatures), such that sediment PAH signatures may have beenswamped by these ‘processed coal’ sources.
Sediment contamination by coal can be readily distinguished from other sources using molec-ular markers such as azaarenes, alkylated phenanthrenes (primarily 1- or 3-methylphenanthrene),and chrysene and picene derivatives (Barrick et al. 1984). Other dominant coal components includepristane, C19 and C20 tricyclic diterpanes, retene, tetrahydrochrysenes and hydropicenes. In anextensive analysis of 16 Washington coals, Barrick et al. (1984) found that increasing rank (i.e.,lignite to anthracite) increased the proportion of low molecular weight n-alkanes relative to otheraliphatic hydrocarbons. Increasing rank furthermore increased the proportion of unsubstituted PAHsrelative to alkylated homologues (e.g., napthalene vs. methylnapthalenes) and increased 3-ringazaarenes relative to 2-ring azaarenes. Lower rank coals tended to be dominated by retene and hadlow quantities of the PAH phenanthrene. Interestingly, Barrick et al. (1984) found only traceamounts of unsubstituted 4- to 7-ring PAHs in Washington coals (except in highest ranked coals).These high molecular weight PAHs, which include well-known compounds such as fluoranthene,pyrene and benzo(a)pyrene, are generally indicative of combustion sources and tend to dominatethe PAH signature of marine sediments near urban areas (Latimer & Zheng 2003). Coal hydrocarbonsignatures can furthermore be distinguished from petroleum by the absence of an unresolvedcomplex mixture (UCM) bulge in their gas chromatograms. Gerhart et al (1980) measured phenolconcentrations of 0.16 mg l–1 in leachates of sub-bituminous coal from the Western U.S., whileFeatherby & Dodd (1977) found considerably lower concentrations (<0.001–0.012 mg l–1) of phenolin coal pile drainage from a Canadian power plant.
In studies of simulated rainfall on coal stockpiles, the highest concentrations of PAHs occurredduring the ‘first flush’ events, when concentrations of suspended solids in the runoff were highest(Fendinger et al. 1989). PAHs that commonly occur in measurable concentrations in coal leachatesinclude naphthalene, phenanthrene, chrysene, fluoranthene and pyrene (Table 5). In a leaching studyof four types of coals (spanning lignitic to bituminous rank), Stahl et al. (1984) noted that morePAHs were leached from sulphur-rich bituminous coals than from low sulphur sub-bituminous coalor lignite, although no correlation between sulphur content and leachate concentration was found
MICHAEL J. AHRENS & DONALD J. MORRISEY
90
Tabl
e 5
Phys
icoc
hem
ical
pro
pert
ies
of c
oal
leac
hate
s. O
rgan
ics
Type
of
leac
hate
Coa
l ty
pe
or o
rigi
nSu
lphu
r%
dw
Stud
y lo
catio
n
Susp
ende
dso
lids
mg
l–1
Filtr
atio
npr
oced
ure
AC
Eµg
l–1
BaA
µg l–1
BaP
µg l–1
BkF
µg l–1
CH
Rµg
l–1
FLT
µg l–1
FL µg l–1
PHE
µg l–1
NA
Pµg
l–1
PYR
µg l–1
DO
Cm
g l–1
Σ A
rom
µg l–1
Ref
.
Stoc
kpile
ru
noff
n.a.
n.a
Fiel
d C
anad
a21
88 ±
34
02U
nfilte
red
71 ±
85
a
47 ±
49
a
208
±
254a
284
±
339a
140
±
173a
1
Stoc
kpile
ru
noff
n.a
n.a
Fiel
d C
anad
adi
ssol
ved
Wha
tman
#1
0.9
±
0.2
0.7
±
0.2
4.5
± 2
.16.
1 ±
3.
33.
1 ±
1.
41
Sim
ulat
ed
rain
run
off
B Illin
ois
#6
>2%
Lab
extr
acte
d1
kg c
oal
Gla
ss w
ool
12
0.6
0.6
13
540
– 4820
–33
42
Sim
ulat
ed
rain
run
off
B K
entu
cky
>2%
Lab
extr
acte
d 1
kg c
oal
Gla
ss w
ool
118
2
Sim
ulat
ed
rain
run
off
SB N
erco
Mon
tana
<2%
Lab
extr
acte
d 1
kg c
oal
Gla
ss w
ool
0.7–
62
Sim
ulat
ed
rain
run
off
L Texa
s1–
3%L
abex
trac
ted
1 kg
coa
lG
lass
woo
l0.
6– 1.2
2
Sim
ulat
ed
rain
run
off
? Mon
tana
?
Lab
extr
acte
d 9
kg c
oal
n.a.
1516
143
in
2
Sim
ulat
ed
rain
run
off
Penn
sylv
ania
&
Mar
ylan
d2–
5%L
abex
trac
ted
6.8
kg
coal
Wha
tman
G
FC0.
06–
0.47
0.15
–0.
290.
06–
0.19
0.04
–0.
970.
01–
0.33
1–28
0.9– 16
.74
Sim
ulat
ed
rain
run
off
Penn
sylv
ania
&
Mar
ylan
d2–
5%L
abSu
spen
ded
0.08
–2.
260.
12–
11.2
00.
5– 5.76
0.10
–2.
780.
05–
3.58
0.07
–5.
220.
10–
5.15
0.4– 32
34
Stoc
kpile
ru
noff
Penn
sylv
ania
&
Mar
ylan
d2–
5%Fi
eld
U.S
.Fi
ltere
d29
34–9
54
Stoc
kpile
ru
noff
Penn
sylv
ania
&
Mar
ylan
d2–
5%Fi
eld
U.S
.Su
spen
ded
5–42
4
91
UNBURNT COAL IN THE MARINE ENVIRONMENT
Stoc
kpile
ru
noff
Can
ada
Fiel
d C
anad
a10
0Se
ttled
SW
le
acha
te0.
285
0.23
30.
417c
0.46
6b0.
353
0.28
2.03
70.
408
0.37
35
Sim
ulat
ed
runo
ffSB
Low
L
ab0.
8% w
/w0.
45 µ
m13
–27
6
SW
leac
hate
Vir
gini
an.
a.L
ab1–
10 m
g l–1
Filte
red
<0.
001
0.2
0.1
7
Gui
delin
esM
OE
E10
144
4610
295
85in
1
AN
ZE
CC
FW 1
6SW
70
8
CW
QG
5.8
0.01
80.
015
n.r.
0.04
30.
4FW
1.1
SW
1.4
0.02
59
NO
AA
SQui
RT
–ac
ute,
SW
FW 1
700
SW 9
7030
030
030
030
0FW
398
0SW
40
300
FW 3
0SW
7.7
FW 2
300
SW 2
350
300
10
Abb
revi
atio
ns: n
.a. =
not
ana
lyse
d; ?
= n
o in
form
atio
n av
aila
ble;
a =
tota
l con
cent
ratio
n in
µg
g–1 o
rgan
ic c
arbo
n; b =
incl
udin
g tr
iphe
nyle
ne; c =
sum
of b
enzo
(b)fl
uora
nthe
ne a
nd b
enzo
(k)fl
uora
nthe
ne;
B =
bitu
min
ous;
L =
lig
nite
; SB
= s
ub–b
itum
inou
s; ±
= m
ean
± st
anda
rd d
evia
tion;
FW
= f
resh
wat
er;
SW =
sea
wat
er;
FLT
= fl
uora
nthe
ne;
PHE
= p
hena
nthr
ene;
BaP
= b
enzo
(a)p
yren
e; P
YR
=py
rene
; C
HR
= c
hrys
ene;
NA
P =
nap
htha
lene
; FL
= fl
uore
ne;
BaA
= b
enz(
a)an
thra
cene
; B
kF =
ben
zo(k
)fluo
rant
hene
; AC
E =
ace
naph
then
e; D
OC
= d
isso
lved
org
anic
car
bon;
Σ A
rom
. =
tot
alar
omat
ic h
ydro
carb
ons;
MO
EE
= M
inis
try
of th
e E
nvir
onm
ent a
nd E
nerg
y gu
idel
ine
(Ont
ario
, Can
ada)
for
par
ticul
ate
boun
d PA
H; t
aken
fro
m C
urra
n et
al.
(200
0), w
ith c
orre
cted
uni
ts; A
NZ
EC
C =
Aus
tral
ian
and
New
Zea
land
Gui
delin
es f
or F
resh
and
Mar
ine
Wat
er Q
ualit
y (2
000)
; tri
gger
leve
l for
pro
tect
ion
of 9
5% o
f sp
ecie
s; C
WQ
G =
Can
adia
n W
ater
Qua
lity
Gui
delin
es f
or th
e Pr
otec
tion
of A
quat
ic L
ife
(200
2);
NO
AA
SQ
uiR
T =
NO
AA
Scr
eeni
ng Q
uick
Ref
eren
ce T
able
s fo
r O
rgan
ics.
Ref
eren
ces:
1 C
urra
n et
al.
2000
, 2 S
tahl
et a
l. 19
84, 3
Wac
hter
& B
lack
woo
d 19
78, 4
Fen
ding
er e
t al.
1989
, 5 C
ampb
ell
& D
evlin
199
7, 6
Ger
hart
et a
l. 19
80, 7
Ben
der
et a
l. 19
87, 8
AN
ZE
CC
2000
, 9
Env
iron
men
t C
anad
a 20
02,
10 B
uchm
an 1
999
MICHAEL J. AHRENS & DONALD J. MORRISEY
92
in a subsequent study (Fendinger et al. 1989). Stahl et al. (1984) also noted that many of the organiccompounds known to exist in raw coal, such as alkenes, alkyl benzenes, alkyl phenols, were notdetected in their laboratory leachates, which was attributed to poor extraction efficiency of theleaching medium (distilled water). Schulz (1997) showed that extraction of phenolic compoundsfrom coal dust by aqueous solutions could be greatly enhanced by the addition of surfactants suchas lecithin. In general, the hydrocarbon concentrations (primarily PAHs) that have been measuredin filtered leachates have been much less than 50 µg l–1, and are typically less than 5 µg l–1. It islikely that the overall poor solubility of PAHs limits substantially higher concentrations in leachates.Assuming a maximum concentration of 50 µg l–1 for an individual PAH compound, Stahl et al.(1984) estimated an average-sized coal stockpile (ca 105 t) to release 2–3 g of that PAH as runoffyr–1. The derivation of this number is obscure, however.
Because PAHs are poorly water soluble and highly hydrophobic, they have a high affinity forparticles, and especially for the hydrophobic domains of organic matter or condensed forms ofcarbon (Bucheli & Gustafsson 2000). Thus, coal runoff containing suspended coal has considerablyhigher PAH concentrations than filtered leachates (Tables 3 and 5). It should also be noted thatPAHs leached from particulate coal are subject to volatilisation, photodegradation and bacterialdegradation that could diminish dissolved concentrations before they reach the receiving waters.
Even though the toxicity of PAHs is well recognised (Di Toro & McGrath 2000, Di Toro et al.2000), water quality guideline values exist for only a handful of compounds (Table 5) and differgreatly between different sets of guidelines. PAHs as a class of contaminant share a similar modeof action (narcosis), so that the toxicity of mixtures of PAHs should be additive (Verhaar et al.1992). Thus, while concentrations of individual PAHs in coal leachates may be below the respectiveEC50 (i.e., the effects concentration leading to a response in 50% of the test organisms), it is possible
Table 6 Concentrations of trace metals in colliery waste and tailings dumped at beach and offshore sites in northeast coast of England, and of waste washed up on the beaches of the area. Sediment quality guidelines from several sources are shown for comparison. All values are µg g–1.
Type of material Cd Cr Cu Hg Ni Pb Zn Reference
Colliery waste <90 µm 2 13 90 1 52 110 100 Norton 1985Colliery waste 90–500 µm 2 5 120 43 230 540 Norton 1985Tailings <500 µm 0.72–0.79 18–29 30–50 0.05–0.10 38–40 52–72 54–68 Limpenny
et al. 1992a
Waste on shore 0.01 0.38 0.54 0.45 0.65 0.1 Hyslop et al. 1997
Whole sediment 0.6 51 54 0.24 34 75 190 Limpenny et al. 1992b
ANZECC ISQG–low 1.5 80 65 0.15 21 50 200 ANZECC 2000
ANZECC ISQG–high 10 370 270 1 52 220 410 ANZECC 2000
NOAA/Environment Canada ISQG
0.7 52.3 18.7 0.13 n.e. 30.2 124 Persaud et al. 1993c
NOAA/Environment Canada PEL
4.2 160 108 0.7 n.e. 112 271 Persaud et al. 1993c
Abbreviations: Empty cell = not analysed; n.e. = not established; ISQG = Intermediate Sediment Quality Guidelines; PEL =Probable Effect Level
Notes: a range of 2 values, b maximum value from 11 samples taken near beach disposal point, c derived from the samesource as NOAA guidelines: Buchman 1999.
UNBURNT COAL IN THE MARINE ENVIRONMENT
93
that the summed concentrations of PAHs may approach toxic levels for undiluted leachate. Whileadditivity of PAH toxicity has been corroborated in laboratory studies with mixtures of purecompounds (Swartz et al. 1997), this phenomenon has not been confirmed for PAHs in coal pileleachates. Furthermore, the majority of PAHs in coal pile leachates has been found to be associatedwith particulate material, whereas dissolved concentrations are commonly low (<5 µg l–1). Forexample, Leppard et al. (1998) found that more than 95% of the water-borne PAHs in a coal-impacted harbour were associated with suspended flocs. This is likely to reduce their bioavailability,as discussed below. To date, there is no published evidence of direct PAH toxicity to marineinvertebrates from particulate coal or coal leachates.
Radioactivity
Unburnt coal contains uranium and thorium, and a variety of radioactive isotopes from the naturaldecay series of 238U, 235U and 232Th, along with traces of 40K (Swaine 1990). Concentrations of Thand U for most types of coal range between 0.5–10 ppm and 0.5–20 ppm, respectively (Swaine1990), and are generally similar to or lower than concentrations in soil and other sedimentary strata.Nevertheless, some coals in India may contain up to 100 ppm U, and up to 2% U has been measuredin coal from Colorado and adjacent regions in the eastern Rocky Mountains (summarised in Swaine1990, Tadmor 1986). Highest concentrations of radioactive elements have typically been measuredin lower rank coals, such as lignite. Hedvall & Erlandsson (1996) summarise average activity massconcentrations of 50, 20 and 20 Bq kg–1 for 40K, 238U and 232Th for unburnt coal. Most studies concernedwith radioactivity from coal have focused on the release of radionuclides during the combustionprocess, which tends to concentrate heavier radioactive elements in the fly ash. Average activitymass concentrations in escaping coal fly ash, estimated by Hedvall & Erlandsson (1996), rangebetween 70–1700 Bq kg–1 for eight radionuclides. There are no explicit studies in the literature onthe aqueous leachability of radioactivity from unburnt coal, such as from storage piles, but it isreasonable to assume that the released radioactivity will be lower than in fly ash, where the entirecoal matrix is destroyed. McDonald et al. (1992), conducting a nationwide survey of radioactivityin coastal U.K. sediments, found a 710-fold concentration of 238U relative to sea water in sedimentsat a site receiving coal spoils from a local colliery, compared with concentration factors of approx-imately 100 for sediments away from direct industrial inputs. Concentration factors for 210Pb and210Po were approximately 1900, compared with 300–650 for a nearby, coal-free sediment sample.While the study reported concentration factors for marine biota (seaweed, mussels and winkles;no species names given) at other sites, no bioaccumulation data were collected for the colliery site.However, assuming similar bioavailability of these radioactive elements in coal-laced sediments asin other sediments, concentration factors in biota would be expected to be 10 times lower for 210Pband 238U and of similar magnitude or up to an order of magnitude higher for 210P. Given thatconcentrations of radioactive elements in coal are of a similar order of magnitude as in soil orshale, and assuming a similarly low bioavailability, biological effects from the traces of radioactivityin coal can be considered highly unlikely.
Toxic effects of unburnt coal and leachates on aquatic organisms
In marked contrast to coal’s well-documented potential to cause adverse physical effects in aquaticorganisms, as reviewed above, there is surprisingly little published evidence demonstrating directtoxic effects of unburnt coal to marine organisms and communities (published information oneffects of unburnt coal on aquatic organisms is summarised in Table 7). This paucity of evidenceseems to uphold the hypothesis that unburnt coal is an ecotoxicologically relatively inert substance(Chapman et al. 1996a). On the other hand, the scarcity of evidence for toxic effects of coal in the
MICHAEL J. AHRENS & DONALD J. MORRISEY
94
Tabl
e 7
Eff
ects
of
unbu
rnt
coal
, in
clud
ing
leac
hate
s, o
n aq
uatic
org
anis
ms
Spec
ies
Exp
erim
ent
type
Exp
osur
e co
nditi
onC
oal
type
Coa
l co
ncen
trat
ion
Ass
umed
st
ress
orO
bser
ved
effe
ctR
efer
ence
Fres
hwat
er a
lgae
Lab
Cen
trif
uged
le
acha
teSu
b-bi
tum
inou
s,
Mon
tana
, U
.S.
3–20
% v
/vV
olat
ile o
rgan
ic
com
poun
dsSt
imul
atio
n of
alg
al g
row
th b
y co
al
leac
hate
s an
d ch
ange
s in
spe
cies
co
mpo
sitio
n. G
row
th in
hibi
tion
by
coal
dis
tilla
tes
in c
lose
d co
ntai
ners
, w
hich
dis
appe
ared
upo
n ae
ratin
g co
ntai
ners
, pos
sibl
y du
e to
rem
oval
of
vol
atile
s. I
n fie
ld m
esoc
osm
s,
1–20
% v
/v d
istil
late
con
cent
ratio
ns
incr
ease
d al
gal
and
bact
eria
l nu
mbe
rs a
nd k
illed
zoo
plan
kton
Ger
hart
et a
l. 19
80
Gre
en a
lga
(Ulv
a la
ctuc
a)L
abSu
spen
ded
colli
ery
was
teN
E E
ngla
nd,
U.K
.29
% b
y w
eigh
t in
was
te,
1 g
l–1
susp
ende
d w
aste
Abr
asio
n by
pa
rtic
ulat
esR
educ
ed g
row
th i
n pr
esen
ce o
f w
aste
and
wat
er m
ovem
ent
but
incr
ease
d gr
owth
with
was
te u
nder
st
ill c
ondi
tions
Hys
lop
&
Dav
ies
1998
Duc
kwee
d (L
emna
m
inor
) (f
resh
wat
er)
Lab
& fi
eld
Unfi
ltere
d sl
urry
Wes
tern
Coa
l N
o. 1
, U
.S.
16.6
–83.
3 g
l–1M
etal
s,
susp
enso
ids
Sim
ilar
grow
th o
ver
16 d
com
pare
d to
con
trol
s; g
reat
er
bioa
ccum
ulat
ion
of s
ome
met
als
(Ba,
Co,
Cu,
Zn)
.
Cow
ard
et a
l. 19
78
Man
grov
e (A
vice
nnia
mar
ina)
, So
uth
Afr
ica
Fiel
dA
irbo
rne
coal
n.d
n.d.
Lig
ht r
educ
tion
Red
uced
CO
2 exc
hang
e by
17–
39%
, de
crea
sed
phot
osyn
thet
ic
perf
orm
ance
Nai
doo
&
Chi
rkoo
t 20
04D
epos
it–fe
edin
g po
lych
aete
(A
reni
cola
mar
ina)
,N
E E
ngla
nd
Fiel
dD
epos
ited
colli
ery
was
teN
E E
ngla
nd,
U.K
.11
% o
f se
dim
ent
by w
eigh
tPh
ysic
al
dest
abili
satio
n of
sed
imen
t by
par
ticul
ates
Wor
ms
avoi
ded
inge
stin
g co
al
part
icle
s du
ring
dep
osit
feed
ing
(pos
sibl
y on
the
bas
is o
f pa
rtic
le
size
); a
void
ance
of
cont
amin
ated
se
dim
ents
in
choi
ce t
ests
; re
duce
d ab
unda
nce
Hys
lop
&
Dav
ies
1999
Cra
b (C
ance
r m
agis
ter)
Lab
Dep
osite
d (a
nd
susp
ende
d?)
coal
n.d.
Up
to 5
0% o
f se
dim
ent
by
wei
ght
Smot
heri
ng o
f gi
lls b
y pa
rtic
ulat
es
Acc
umul
atio
n of
coa
l in
gill
s at
hi
gher
con
cent
ratio
nsPe
arce
&
McB
ride
19
77
95
UNBURNT COAL IN THE MARINE ENVIRONMENT
Cra
b (C
ance
r m
agis
ter)
Lab
Dep
osite
d (a
nd
susp
ende
d?)
coal
n.d.
Up
to 7
5% o
f se
dim
ent
by
volu
me
Smot
heri
ng o
f gi
lls b
y pa
rtic
ulat
es
No
mea
sura
ble
diff
eren
ce i
n ve
ntila
tion
and
oxyg
en
cons
umpt
ion
over
21
d re
lativ
e to
co
ntro
ls
Hill
aby
1981
Mar
ine
pred
ator
y sn
ail
(Hex
aple
x tr
uncu
lus)
, Is
rael
Lab
& fi
eld
Coa
l se
dim
ent
n.d.
n.d.
Cd
from
dir
ect
cont
act
Snai
ls f
rom
coa
l–im
pact
ed s
ite h
ad
1.8
times
hig
her
Cd
conc
entr
atio
ns
in h
epat
opan
crea
s, u
p to
3.6
tim
es
incr
ease
d ep
ithel
ial
perm
eabi
lity,
re
duce
d ly
soso
me
tran
spor
t an
d 3
times
hig
her m
etal
loth
ione
in le
vels
th
an c
oal–
free
con
trol
s
Sibo
ni e
t al.
2004
Oys
ter
(Cra
ssos
trea
vi
rgin
ica)
Lab
Susp
ende
d co
al
dust
incl
udin
g le
acha
te (
pre-
equi
libra
ted
for
2 w
eeks
)
<40
um
0, 1
and
10
mg
l–1PA
HN
o si
gnifi
cant
adv
erse
eff
ect
on
oyst
er s
urvi
val,
shel
l gr
owth
or
pum
ping
act
ivity
aft
er 2
8 d,
but
cl
ams
in h
ighe
st t
reat
men
t ha
d sl
ight
ly r
educ
ed s
hell
grow
th (
non-
sign
ifica
nce
due
to la
rge
vari
ance
).
No
sign
ifica
nt a
ccum
ulat
ion
of
PAH
s in
tis
sues
of
depu
rate
d oy
ster
s, d
espi
te o
bser
vabl
e in
gest
ion
of c
oal.
How
ever
, no
te
agai
n hi
gh v
aria
nce
in ti
ssue
leve
ls
afte
r 28
d.
Ben
der
et a
l. 19
87
Dep
osit–
feed
ing
biva
lve
(Mac
oma
balt
hica
), A
lask
a
Fiel
dC
oal
in
sedi
men
tsE
rosi
on o
f ex
pose
d co
al
seam
s,
Kac
hem
ak B
ay,
Ala
ska,
U.S
.
n.d.
Satu
rate
d an
d un
satu
rate
d hy
droc
arbo
ns
Ani
mal
s fr
om n
atur
ally
coa
l-co
ntam
inat
ed s
ite c
onta
ined
an
arra
y of
hyd
roca
rbon
s ch
arac
teri
stic
of
the
coal
in
the
sedi
men
t, bu
t an
imal
s w
ere
not
depu
rate
d pr
ior
to a
naly
sis,
so
inge
stio
n an
d as
sim
ilatio
n co
uld
not
be d
istin
guis
hed
Shaw
&
Wig
gs 1
980
Inte
rtid
al
asse
mbl
ages
of
rock
y an
d sa
ndy
shor
es, N
E E
ngla
nd
Fiel
dD
epos
ited
colli
ery
was
teN
E E
ngla
nd,
U.K
.27
% o
f se
dim
ent
by w
eigh
tPh
ysic
al
abra
sion
, de
stab
ilisa
tion
of s
edim
ent b
y pa
rtic
ulat
es
Red
uced
num
ber
of m
acro
alga
l sp
ecie
s on
con
tam
inat
ed r
ocky
sh
ores
, an
d of
mac
roin
vert
ebra
tes
on s
andy
sho
res
Hys
lop
et a
l. 19
97
MICHAEL J. AHRENS & DONALD J. MORRISEY
96
Tabl
e 7
(con
tinu
ed)
Eff
ects
of
unbu
rnt
coal
, in
clud
ing
leac
hate
s, o
n aq
uatic
org
anis
ms
Spec
ies
Exp
erim
ent
type
Exp
osur
e co
nditi
onC
oal
type
Coa
l co
ncen
trat
ion
Ass
umed
st
ress
orO
bser
ved
effe
ctR
efer
ence
Ben
thic
fau
nal
asse
mbl
ages
, N
E
U.K
.
Fiel
dC
ollie
ry w
aste
du
mpe
d on
the
shor
e
NE
Eng
land
, U
.K.
n.d.
Susp
ende
d an
d de
posi
ted
part
icul
ates
Infil
ling
of c
revi
ce h
abita
ts o
f cr
abs
and
lobs
ters
, re
duce
d ab
unda
nce
and
dive
rsity
of
soft
–sed
imen
t as
sem
blag
es,
with
onl
y m
obile
po
lych
aete
s, a
mph
ipod
s an
d op
hiur
oids
pre
sent
aro
und
one
of
the
larg
er b
each
dum
psite
s
Shel
ton
1973
Subt
idal
sof
t-se
dim
ent
bent
hic
asse
mbl
ages
, N
E
Eng
land
Fiel
dC
ollie
ry w
aste
du
mpe
d on
sea
bed
NE
Eng
land
, U
.K.
Up
to 2
0% i
n w
aste
, and
was
te
repr
esen
ts >
70%
of
sed
imen
t
Susp
ende
d an
d de
posi
ted
part
icul
ates
Red
uced
div
ersi
ty a
nd a
bund
ance
at
site
s w
ith l
arge
am
ount
s of
was
te
pres
ent,
but
effe
cts
of c
ollie
ry
was
te c
onfo
unde
d by
dis
posa
l of
dr
edge
spo
il at
sam
e si
te a
nd b
y di
ffer
ence
s in
wat
er d
epth
. N
o ev
iden
ce o
f up
take
of
met
als
by
com
mer
cial
ly h
arve
sted
fish
and
cr
usta
cean
s
Nor
ton
1985
Subt
idal
sof
t-se
dim
ent
bent
hic
asse
mbl
ages
, N
E
Eng
land
Fiel
dC
ollie
ry w
aste
du
mpe
d on
sea
bed
NE
Eng
land
, U
.K.
1.8–
5.7%
of
sedi
men
t by
w
eigh
t
Susp
ende
d an
d de
posi
ted
part
icul
ates
Red
uced
abu
ndan
ce a
nd d
iver
sity
at
form
er w
aste
dis
posa
l si
tes
com
pare
d w
ith c
ontr
ol s
ite,
with
va
riab
le e
vide
nce
of r
ecov
ery
amon
g im
pact
ed s
ites,
but
one
im
pact
ed s
ite h
ad h
ighe
r di
vers
ity
than
the
con
trol
(6
mon
ths
afte
r ce
ssat
ion
of d
umpi
ng)
John
son
&
Frid
199
5
Inte
rtid
al s
oft-
sedi
men
t be
nthi
c as
sem
blag
es,
NE
E
ngla
nd
Fiel
dC
ollie
ry w
aste
du
mpe
d on
sh
ore
NE
Eng
land
, U
.K.
Up
to 2
0% i
n w
aste
, no
dat
a gi
ven
on
conc
entr
atio
n in
se
dim
ent
Susp
ende
d an
d de
posi
ted
part
icul
ates
Red
uced
abu
ndan
ce a
nd d
iver
sity
at
form
er w
aste
dis
posa
l si
tes
com
pare
d w
ith c
ontr
ol s
ite a
nd
undu
mpe
d si
te w
ith n
earb
y, n
atur
al
sour
ce o
f co
al,
with
var
iabl
e ev
iden
ce o
f re
cove
ry a
mon
g im
pact
ed s
ites
Bar
nes
& F
rid
1999
97
UNBURNT COAL IN THE MARINE ENVIRONMENT
Inte
rtid
al s
oft-
sedi
men
t be
nthi
c as
sem
blag
es,
Bri
tish
Col
umbi
a,
Can
ada
Fiel
dC
oal
in
sedi
men
tsB
itum
inou
s co
al
from
wre
cked
co
llier
4.35
% o
f se
dim
ent
(as
TO
C)
Dep
osite
d pa
rtic
ulat
esC
hang
es i
n be
nthi
c as
sem
blag
e at
si
tes
whe
re c
oal p
rese
nt, a
ttrib
uted
to
gra
in-s
ize
effe
cts
rath
er th
an th
e to
xici
ty o
f co
al-d
eriv
ed P
AH
(w
hich
sho
wed
litt
le
corr
espo
nden
ce w
ith s
edim
ent
toxi
city
)
Cha
pman
et
al.
1996
a
Ben
thic
fau
nal
asse
mbl
ages
, Sv
alba
rd
Fiel
dC
oal
in
sedi
men
tsSv
alba
rdn.
d.Fi
ne s
edim
ent
Hig
h co
ncen
trat
ions
of
PAH
pre
sent
in
sed
imen
ts,
pres
umed
to
be
deri
ved
from
run
off
from
coa
l st
ores
and
gen
eral
ind
ustr
ial
activ
ity.
Low
fau
nal
dive
rsity
and
do
min
ance
by
spec
ies
char
acte
rist
ic o
f or
gani
cally
en
rich
ed a
reas
attr
ibut
ed to
eff
ects
fr
om d
epos
ition
of
fine
-gra
ined
gl
acia
l sed
imen
ts, u
ntre
ated
sew
age
inpu
ts a
nd g
arba
ge d
ump
leac
hate
.
Hol
te e
t al.
1996
Stre
am i
nver
tebr
ate
asse
mbl
ages
, Sou
th
Wal
es,
U.K
. (f
resh
wat
er)
Fiel
dSu
spen
ded
and
depo
site
d st
ockp
ile
runo
ff
Sout
h W
ales
, U
.K.
n.d.
Silta
tion
by c
oal
part
icul
ates
, lo
w p
H,
trac
e m
etal
s
Red
uced
fau
nal
abun
danc
e an
d di
vers
ity i
n bo
th p
H-a
ffec
ted
and
sedi
men
t-af
fect
ed s
tret
ches
of
the
stre
am, w
ith v
aria
ble
susc
eptib
ility
am
ong
taxa
, w
ith E
phem
erop
tera
, Pl
ecop
tera
and
Tri
chop
tera
mos
t su
scep
tible
and
bur
row
ers,
e.g
., ch
iron
omid
larv
ae a
nd o
ligoc
haet
es
leas
t
Scul
lion
&
Edw
ards
19
80
Stre
am i
nver
tebr
ate
asse
mbl
ages
, ea
ster
n U
.S.
(fre
shw
ater
)
Fiel
dC
oal-
pile
run
off
Eas
tern
U.S
.n.
d.T
race
met
als,
lo
w p
HR
educ
ed f
auna
l di
vers
ity a
ttrib
uted
to
com
bina
tion
of e
ffec
ts o
f pe
riod
ic d
roug
ht a
nd c
oal-
pile
ru
noff
Swif
t 19
85
MICHAEL J. AHRENS & DONALD J. MORRISEY
98
Tabl
e 7
(con
tinu
ed)
Eff
ects
of
unbu
rnt
coal
, in
clud
ing
leac
hate
s, o
n aq
uatic
org
anis
ms
Spec
ies
Exp
erim
ent
type
Exp
osur
e co
nditi
onC
oal
type
Coa
l co
ncen
trat
ion
Ass
umed
st
ress
orO
bser
ved
effe
ctR
efer
ence
Fath
ead
min
now
(P
imep
hale
s pr
omel
as)
Lab
Susp
ende
d co
al,
spik
ed w
ith
phen
anth
rene
Sub–
bitu
min
ous,
D
ecke
r, M
onta
na,
U.S
.
10–2
0 m
g l–1
Abr
asio
nN
o ch
ange
s to
gut
and
gill
ep
ithel
ium
and
no
chan
ges
to
grow
th r
ate
over
a 1
4-d
peri
od;
pron
ounc
ed m
ucus
and
coa
l ac
cum
ulat
ion
in g
ut, b
ut r
apid
gut
cl
eara
nce
afte
r ex
posu
re;
no
diff
eren
ce i
n ph
enan
thre
ne u
ptak
e be
twee
n co
al t
reat
men
ts a
nd
part
icle
-fre
e co
ntro
ls
Ger
hart
et a
l. 19
81
Fath
ead
min
now
(P
imep
hale
s pr
omel
as)
Lab
Cen
trif
uged
and
un
cent
rifu
ged
leac
hate
s
Sub-
bitu
min
ous,
M
onta
na,
U.S
.6.
3 g
l–1
cent
rifu
ged;
25
g l–1
un
cent
rifu
ged
PAH
s10
0% m
orta
lity
in u
ncen
trif
uged
le
acha
te a
fter
96
h. N
o in
crea
sed
mor
talit
y of
juv
enile
s or
adu
lts
expo
sed
to c
entr
ifug
ed le
acha
te fo
r 3–
24 w
eeks
; gro
wth
rat
e si
mila
r to
co
ntro
ls,
but
onse
t of
mat
urity
de
laye
d; 3
6% s
paw
ning
suc
cess
in
leac
hate
s vs
. 90
% i
n co
ntro
ls;
Som
e qu
alita
tive
diff
eren
ces
in G
C
anal
yses
of
tissu
e ex
trac
ts
Car
lson
et a
l. 19
79
Bul
lhea
d ca
tfish
, ra
inbo
w t
rout
(I
ctal
urus
ne
bulo
sus
and
Onc
orhy
nchu
s m
ykis
s ga
irdn
eri)
Lab
Coa
l he
avy
dist
illat
e an
d de
rive
d fr
actio
ns
Mix
ed w
ith w
ater
10 m
g l–1
Hyd
roca
rbon
sPa
thol
ogic
al r
espo
nses
(hy
perp
lasi
a an
d en
gorg
emen
t of
blo
od v
esse
ls
of g
ill t
issu
e, c
hang
es t
o m
itoch
ondr
ia a
nd r
ough
en
dopl
asm
ic r
etic
ulum
),
part
icul
arly
in
rain
bow
tro
ut
Stok
er e
t al.
1985
Rai
nbow
tro
ut
(Onc
orhy
nchu
s m
ykis
s ga
irdn
eri)
Lab
Susp
ende
d co
al12
0–60
0 m
g l–1
Mec
hani
cal
irri
tatio
nC
ough
rat
e in
crea
sed
twof
old
Hug
hes
1975
99
UNBURNT COAL IN THE MARINE ENVIRONMENT
Rai
nbow
tro
ut
(Onc
orhy
nchu
s m
ykis
s ga
irdn
erii
)
Lab
Susp
ende
d co
al
was
hing
sN
ottin
gham
shir
e,
U.K
., co
al
was
hing
s
200
mg
l–1M
echa
nica
l ir
rita
tion
No
toxi
c ef
fect
s bu
t red
uced
gro
wth
ov
er a
10-
mon
th p
erio
dH
erbe
rt &
R
icha
rds
1963
Rai
nbow
tro
ut
(Onc
orhy
nchu
s m
ykis
s ga
irdn
eri)
Lab
Cen
trif
uged
le
acha
teSu
b–bi
tum
inou
s,
Mon
tana
, U
.S.
6.3
g l–1
ce
ntri
fuge
d;PA
Hs
No
pron
ounc
ed d
iffe
renc
es i
n liv
er
para
met
ers:
liv
er w
eigh
t, he
patic
m
icro
som
al p
rote
in,
DN
A c
onte
nt
and
AH
H a
ctiv
ity a
fter
28
d; n
o co
nsis
tent
incr
ease
in h
epat
ic A
HH
ac
tivity
and
cyt
ochr
ome
P450
co
nten
t ove
r 21
d up
on e
xpos
ure
to
coal
ste
am d
istil
late
s
Car
lson
et a
l. 19
79
Chi
nook
sal
mon
(Onc
orhy
nchu
s ts
haw
ytsc
ha)
Lab
Susp
ende
d co
aln.
d.60
–500
mg
l–1PA
Hs
Incr
ease
d C
YP1
A1
and
ribo
som
al
prot
ein
L5
expr
essi
on i
n liv
erC
ampb
ell
&
Dev
lin 1
997
Stee
lhea
d an
d cu
tthro
at t
rout
(O
ncor
hync
hus
myk
iss
and
O. c
lark
ii),
eas
tern
U
.S.
(fre
shw
ater
)
Fiel
dSu
spen
ded
coal
Was
hing
ton,
U.S
.22
.5 g
l–1
(?)
Mec
hani
cal
irri
tatio
n by
pa
rtic
ulat
es
Mor
talit
y af
ter
0.5–
2.5
h ex
posu
res
to s
uspe
nded
coa
l w
ashi
ng i
n a
stre
am
Paut
zke
1937
Eig
ht fi
sh s
peci
es,
incl
udin
g br
own
trou
t (S
alm
o tr
utta
)So
uth
Wal
es,
U.K
. (f
resh
wat
er)
Fiel
dSu
spen
ded
coal
w
ashi
ngs
SE W
ales
, U
.K.
TSS
up
to
1530
mg
l–1
Susp
ende
d so
lids
Fish
den
sitie
s of
all
spec
ies
exce
pt
trou
t de
clin
ed d
owns
trea
m o
f di
scha
rge;
no
spaw
ning
in
mai
n tr
unk
of r
iver
; po
or g
row
th o
f tr
out
Will
iam
s &
H
arcu
p 19
74
n.d.
= n
o da
ta.
MICHAEL J. AHRENS & DONALD J. MORRISEY
100
marine environment could also reflect a limited research effort in this area. Indeed, most studieson the effects of unburnt coal on aquatic biota have been done in freshwater. Given the extensivecompositional heterogeneity of coal and the diversity of weathering and exposure conditions, itseems improbable that coal as a whole can be labelled as ‘toxicologically benign’. One generalproblem of toxicological studies is that toxic effects may occur at various biological and temporalscales, from molecular to ecosystem-wide, or from short-term to chronic, which makes resultsdependent on the chosen scale of observation. Furthermore, it is often difficult, if not impossible,to separate toxic effects from physically induced stress. For example, several field studies infreshwater have observed reductions in abundance, diversity, growth and reproduction of fishes andmacroinvertebrates, which were attributed to physical stress to organisms by suspended coal par-ticles (Herbert & Richards 1963, Williams & Harcup 1974, Scullion & Edwards 1980). In theabsence of a direct and definable causal mechanism, chemical toxicity cannot be ruled out.
The following discussion assesses factors that influence the bioavailability of toxicants in coaland then reviews information on the response of aquatic biota to unburnt coal at three differentbiological levels: (1) cellular, (2) organism and (3) populations and assemblages. Toxicologicaleffects, like physical effects, can act both directly and indirectly. Indirect effects include responsesof populations to changes in the abundances of predators, prey or competitors caused by contaminanttoxicity (Chapman 2004). Chapman (2004) pointed out that indirect effects are mainly associatedwith ecosystem function rather than structure but that function is rarely determined in ecologicalrisk assessments.
Factors that influence coal toxicity — dilution, buffering and bioavailability
As the previous discussion has shown, coal contains a plethora of compounds that may be leachedupon contact with water and that have the potential to cause toxic effects to aquatic biota. Theamount of material that is leachable crucially depends on the coal type, mineral impurities andleaching conditions. For example, low-rank coals, such as brown coals, lignites and sub-bituminouscoals, contain a large fraction of mineral matter in pore waters and associated with the organiccompounds of the coal macerals, which are often readily leachable with water. In higher rankcoals, such as bituminous coals and anthracite, expulsion of moisture and associated dissolvedminerals, combined with changes in the chemical structure of the organic matter, tend to removethese non-mineralised inorganics, so that the majority of inorganic impurities are typically presentas particulate minerals, discrete from the coal macerals (Ward 2002). Whether potentially toxiccomponents of coal actually exert a negative impact on aquatic biota is determined by their bioavail-ability and the concentration they attain in the receiving environment. Thus, even though trace metalsmay be leached from coal piles, their concentrations after dilution by large volumes of water, suchas coastal seas, may become negligible compared with other sources. Furthermore, formation ofinsoluble salts upon contact with sea water, complexation by dissolved organic matter in sea wateror in coal leachates (Table 5), adsorption onto particle surfaces, or redox reactions that result inchanges of speciation or solubility may render metals leached from coal biologically unavailable.Metals and metalloids that are readily soluble under low pH conditions, such as Cd, Cu, Pb, Zn andAs may become insoluble upon contact and dilution of leachates with alkaline sea water. On the otherhand, particle-bound metals and metalloids that are soluble under alkaline conditions, such as Cr andSe, may become solubilised upon contact with sea water. With the exception of a study by Duedallet al. (1982) on compacted coal waste material, no attempts have been made to measure the releaseof metals from coal deposited on the sea floor. Biggs et al. (1984) speculated that the combinationof acidic and low redox conditions in sediments could favour metal release from coal and subsequentuptake by benthic organisms but no experimental studies have attempted to test this hypothesis.
UNBURNT COAL IN THE MARINE ENVIRONMENT
101
Analogous to trace metals, bioavailability and toxicity of organic constituents of coal are largelydependent on the degree to which they are adsorbed onto suspended or deposited particles (Meadoret al. 1995). Because only a few studies have documented direct effects of organic compounds incoal (Table 7), it has been argued that coal constitutes essentially an inert contaminant (Chapmanet al. 1996a). Coal particles may bind and stabilise PAHs either by incorporation into the solid coalmatrix or by strong adsorption to surfaces that probably act quite similarly to activated carbon(Ghosh et al. 2000, 2001, Talley et al. 2002). The presence of coal in aquatic sediments can thereforeresult in elevated and highly variable PAH and total organic carbon (TOC) concentrations to whichequilibrium partition theory does not apply. Thus, even though PAH concentrations in such coal-laced sediments may exceed sediment quality guidelines (Long et al. 1995, ANZECC 2000; seeTable 3), the majority are in an unavailable form by being tightly bound to coal particles (Chapmanet al. 1996a, Paine et al. 1996). On the other hand, some studies have found benthic organisms toaccumulate elevated concentrations of PAHs in the vicinity of coal-coking plants (Uthe & Musial1986) and coal-fired power stations (Eadie et al. 1982), although the accumulated PAHs may haveoriginated from combustion or coalification processes rather than from unburnt coal. In a Canadianstudy on environmental impacts of coal mines and coal-fired power stations on sediment quality,Cheam et al. (2000) observed highest toxicity to chironomids and amphipods from sediment thatwas collected downstream of a colliery and that contained high levels of PAHs relative to othersites sampled (e.g., 4 µg g–1 naphthalene, 3.4 µg g–1 by dry weight of phenanthrene and severalother PAHs with concentrations between 0.1–1.0 µg g–1 by dry weight). In contrast, other inverte-brates tested (mayflies and tubificids) showed no or little decrease in survival, growth and repro-duction. Because sediment trace metal concentrations in colliery sediment were similar to othersites, the observed toxicity may have been the result of PAH contamination.
Despite the strong partitioning of PAHs to particulate matter, PAHs do desorb from coal intoclean water to a measurable extent. For example, several µg l–1 of total PAH have been measuredin filtered coal leachates (Table 5; Stahl et al. 1984, Fendinger et al. 1989), yet these concentrationsgenerally fall well below water quality guidelines. PAHs potentially derived from coal have beenfound to accumulate in animal tissues by Paine et al. (1996), who measured elevated PAH levelsin the hepatopancreas of Cancer magister in an inner harbour area contaminated by coke and pitchparticles. However, it is quite likely that the main sources of these accumulated PAHs were modifiedcoal products (coal tar, coke) rather than unburnt coal. Furthermore, despite being measurable inanimal tissues, these concentrations did not lead to differences in growth, size, catch-per-unit effortor condition. Interestingly, low molecular weight PAHs (LPAH) dominated in crab hepatopancreas,in contrast to the sediment PAH signature, which was dominated by high molecular weight PAHs.The dominance of LPAHs in crab tissue may indicate that it is mostly the very hydrophobic, highmolecular weight PAHs (HPAHs), and not all PAHs in coal, that are unavailable.
It is currently not known what happens to coal-associated contaminants in organism guts, wheresurfactants and other forms of dissolved organic carbon may enhance solubilisation of particle-bound contaminants (Mayer et al. 1996, 2001, Voparil & Mayer 2000). For example, Mayer et al.(1996) found that digestive fluids of deposit feeding macrofauna, such as the sediment-ingestinglugworm Arenicola marina, and the holothurian Parastichopus californicus, solubilised up to 200times more PAHs and up to 2400 times more copper than would be predicted from water-solidpartitioning with clean sea water. Consequently, toxic components that are adsorbed to coal particlesin water and appear to be unavailable might become available upon ingestion and contact with gutfluid. Because different invertebrate species may differ greatly with regard to specific gut fluidcomposition and the potential for solubilising organic contaminants or trace metals (Mayer et al.2001), it is currently impossible to assess accurately the risk of dietary exposure to coal-boundcontaminants for invertebrates inhabiting coal-contaminated sediments.
MICHAEL J. AHRENS & DONALD J. MORRISEY
102
The likelihood of acidic and saline coal leachates affecting terrestrial and aquatic communitieswill depend greatly on the dilution and buffering capacity of the receiving environment. In lightof the enormous buffering capacity of sea water, the changes in pH and salinity in the marineenvironment due to coal leachates are likely to be undetectable. Impacts of high acidity and salinitywill therefore be restricted to the terrestrial environment surrounding, and the culverts and anystreams draining, the coal storage and handling facilities. It seems probable that if acidic coal pileleachate enriched in dissolved metals comes into contact with sea water, the ensuing changes inpH and ionic strength will facilitate flocculation and precipitation of metals and other previouslydissolved or suspended components (Salomons & Förstner 1984). This material is likely to settleout at the point where it enters the marine environment or in nearby sheltered areas. Thus,accumulation of particle-bound metals could potentially be predicted for the mixing zone ofleachates in estuaries (e.g., Williamson & Morrisey 2000, Chapman & Wang 2001).
Effects at the cellular level
Coal dust has been shown to affect PAH-metabolising enzymes in livers of chinook salmon(Oncorhynchus tshawytscha) (Campbell & Devlin 1997). Exposure of fish to coal suspensions of60–500 mg l–1 for 8 days increased expression of CYP1A1, an enzyme of the hepatic cytochromeP450 system, which plays a central role in the cellular detoxification of xenobiotic compoundssuch as PAHs. Furthermore, coal dust induced the expression of a ribosomal protein, L5, whosefunction, however, remains unknown. The induction of CYP1A1 has been used as a sensitivebiomarker for the exposure of animals to organic contaminants such as PAHs. Expression of thisgene does not denote toxicity or cellular damage but rather a cellular biochemical response to toxiccompounds. However, the activation of its cytochrome P450 system represents a double-edgedsword for an animal from a toxicological standpoint. On the one hand, CYP1A1 converts hydro-phobic compounds to more water-soluble derivatives that may be excreted whereas, on the otherhand, while doing so, it may generate more toxic, mutagenic by-products.
Whereas the previous study observed a clear cellular response of fishes to coal leachates,Carlson et al. (1979) found no change in liver parameters in rainbow trout (Oncorhynchus mykissgairdneri) exposed for 28 days to aqueous leachates of sub-bituminous coal from Montana (U.S.):liver weights, microsomal protein and DNA content, and aryl hydrocarbon hydroxylase activity(AHH) varied similarly over 28 days of exposure compared with control fish. Exposure of trout tosteam distillates of coal for 21 days resulted in no PAH bioaccumulation nor significant increasesin hepatic mixed function oxidase (MFO) activity (i.e., AHH activity and cytochrome P450 proteincontent) compared with controls. The reason for this may lie in differences in the type of coal usedor the method of preparing leachates. Whereas Carlson et al. (1979) centrifuged their leachates,Campbell & Devlin (1997) merely allowed coal dust slurries to settle, and noted that the finalleachate contained a significant amount of non-settlable solids. Interestingly, Carlson et al. (1979)observed 100% mortality within 96 h when exposing fathead minnows to uncentrifuged leachates.This provides further evidence that particulate coal has a greater likelihood of causing adversebiological effects than leachates, even though it is difficult to state whether these adverse effectsare due to toxicity or physical irritation. Evidence from the medical literature suggests that PAHscontained in coal dust are not capable of crossing the skin barrier of mammals and are not elutedby pig lung homogenate or human gastric juice (Foa et al. 1998).
Siboni et al. (2004) found that the presence of coal in coastal sediment increased cadmiumconcentrations in tissues of predatory gastropods. This effect was accompanied by increasedmetallothionein levels in tissues, increased paracellular permeability, and impeded lysosomal accu-mulation of lipophilic substances. These sublethal effects were interpreted as evidence for cryptic
UNBURNT COAL IN THE MARINE ENVIRONMENT
103
cellular damage, even though no increased mortalities were evident in the field or in laboratorymanipulations with coal-amended sediment. Metallothioneins play an important role in the detox-ification of metals in invertebrates by converting dissolved metals into an inert, particulate form.Their induction may have been triggered by cadmium present in the coal. Increased permeabilityof membranes, measurable as incorporation of fluorescein dye, is thought to reflect injury ofepithelia and their intercellular junctions, which may have resulted from contact with Cd from thecoal substrate. Paracellular fluorescence was especially enhanced in foot tissue, which would haveexperienced the highest contact time with the coal. Lower lysosomal accumulation of lipid-solublecationic markers, such as neutral red, has been used as a non-specific indicator of cellular damage.
Effects at the organism level
Whereas a number of studies, discussed in the physical effects section above, have shown directadverse effects of coal particulates or leachates on survival, growth and reproduction of fishes anda variety of aquatic invertebrates, there have been only a few studies investigating potential toxiceffects of unburnt coal to marine organisms. The majority of these concluded that unburnt coal orits leachates are not acutely or chronically toxic. For example, Bender et al. (1987) reported that28 days of exposure of eastern oysters (Crassostrea virginica) to suspensions containing 1 and10 mg l–1 coal dust did not affect survival or significantly alter shell growth or pumping activitycompared with controls nor did coal exposure lead to significant bioaccumulation of PAHs in oystertissues. These authors considered that because coal dust was observed in the faeces of the oysters,this indicated that toxic compounds contained in coal were unavailable. This conclusion was alsosupported by the fact that no differences in PAH concentrations were detected between controlwater and coal-water slurries. However, while Bender et al. (1987) convincingly demonstrated noacute toxicity, in terms of mortality, there may have been a major bias in their interpretation of thegrowth and accumulation data. The problem lies with the very high background concentrations ofPAHs in control estuarine water (York River, U.S.) and oyster tissues (from Rappahannock River),which may have ‘swamped’ PAH contributions from coal during the actual experiment. For example,phenanthrene and fluorene concentrations in York River water were 0.6 µg l–1 and 0.3 µg l–1, respec-tively, and total PAH concentrations in control oyster tissues ranged between 1.38–2.27 µg g–1. Incomparison, typical tissue concentrations in oysters from mildly contaminated urban estuaries rangebetween 20–100 ng g–1 (G. Olsen, NIWA, personal communication) and the median tissue ΣPAHconcentration of shellfish monitored under the U.S. NOAA National Status and Trends MusselWatch Program (seven bivalve species) is 230 ng g–1 (O’Connor 2002). This result suggests thatthe oysters from the Rappahannock River used by Bender et al. (1987) may have been highlycontaminated by PAHs prior to exposure to coal. Alternatively, the oysters could have accumulatedthe majority of their PAH tissue burden from York River water over the 28-day exposure period orduring the 3-wk acclimation period. Comparing ratios of individual PAHs to the sum of methyl-phenanthrenes (the dominant PAHs in the coal used) revealed that tissue from coal-exposed,depurated oysters had similar PAH ratios to coal once the high background PAH of control oysterswas subtracted. This comparison indicates, in contrast to the authors’ interpretation, that somePAHs may have indeed accumulated from coal. Bender et al. (1987) also compared weekly shelllength increments in oysters exposed to 0, 1 and 10 mg l–1 suspensions of coal dust and concludedthere was no significant difference in shell growth among treatments on a given sampling date forthe three test populations. However, it should be noted that numerical differences in growth wereindeed observed and that the lack of statistical difference may have been in part due to large variancewithin treatments. Furthermore, when their growth data are re-analysed by regressing weekly shellgrowth vs. days of exposure, the 10 mg l–1 treatment had the lowest slope and the control the
MICHAEL J. AHRENS & DONALD J. MORRISEY
104
highest, suggestive of a treatment effect. Nonetheless, the conclusion remains valid that neithermortality nor markedly reduced growth was observable upon exposure to coal dust, suggestinglimited toxicity of coal dust.
Hillaby’s (1981) finding of no mortality in crabs exposed to coal dust in aquaria, mentionedabove, suggested the absence of a direct acute toxic effect. However, as in many bioassay studiesthere was large variability among individuals within treatments, which may have resulted in lowstatistical power to detect effects. In a study of freshwater fishes, Carlson et al. (1979) observedthat rainbow trout and fathead minnows (Pimephales promelas) exposed to centrifuged coalleachates for 3–24 wk showed no increased mortality, no diminished growth and no pronouncedPAH bioaccumulation. However, a lower spawning success was observed in fathead minnows during2–4 wk exposures. Furthermore, 100% mortality was observed in fishes that were exposed touncentrifuged coal leachates containing suspended coal. In a study in Kachemak Bay, Alaska,deposit feeding clams (Macoma balthica) accumulated an array of hydrocarbons suggesting coalas a source, whereas suspension-feeding mussels (Mytilus edulis) and grazing limpets (Collisellapelta) accumulated hydrocarbons in their tissues that suggested petroleum origin (Shaw & Wiggs1980). It should be noted, however, that the shellfish were not depurated before analysis ofhydrocarbons and consequently the contaminants may only have been present in the digestive tractand not assimilated into tissues. Paine et al. (1996) found no sediment toxicity to amphipods(Rhepoxynius abronius) and sand dollars (Dendraster excentricus) from sediments enriched in cokeparticles or pitch globules in the vicinity of an aluminium smelting plant. While this study did notfocus on unburnt coal but, rather, on thermochemically modified coal products, the absence ofobservable mortality also acts to rule out any potential toxicity from unburnt coal that may havebeen present in these industrially impacted sediments.
Some stimulatory effects of coal have been reported. For example, Gerhart et al. (1980) observedincreased growth and higher chlorophyll a concentration in freshwater algal periphyton exposed tocoal leachates in the laboratory (coal concentration: 3.2% and 17% v/v). The growth stimulationin coal treatments occurred regardless of whether leachates were centrifuged or not and thestimulation was not attributable to differences in total phosphorus concentrations. In the field,however, filtered coal leachates inhibited the growth of test algae, which may have been a resultof differences in the algal species used or container effects (field exposures used glass bottles,whereas laboratory experiments used plastic containers). Coal distillates, produced to mimic theeffect of spontaneous heating in coal storage piles, inhibited growth of algae in a dose-dependentmanner, which was attributed to the presence of volatile organic compounds (alkanes, alkylbenzenesand alkylnaphthalenes). When distillates were bubbled to remove volatile organic compounds,growth stimulation was frequently observed.
Effects at the levels of populations and assemblages
The study by Gerhart et al. (1980) also demonstrated general stimulation of algal growth and shiftsin algal species composition (primarily diatoms) upon exposure of periphyton assemblages to coalleachates in the laboratory. In closed, unaerated containers, algal assemblages showed inhibitedgrowth. Field mesocosms with coal distillates resulted in greater algal growth and chlorophyll a,while reducing zooplankton biomass. The main stressors were believed to be volatile organiccompounds present in distillates.
As far as could be ascertained, there have been no manipulative experimental studies of effectsof coal on populations or assemblages of marine or estuarine organisms in situ. Consequently,evidence of effects has to rely on correlational studies in which abundances and diversities oforganisms are compared among areas containing different amounts of coal. In common with allcorrelational studies, these are subject to confounding by covariation among factors, measured or
UNBURNT COAL IN THE MARINE ENVIRONMENT
105
unmeasured, that may potentially affect the biota, other than the presence of coal. In the case ofcoal, covariables are likely to include patterns of distribution of natural sediments that are subjectto the same sources and mechanisms of transport as the coal. Coal is often dumped or otherwiseenters the marine environment in combination with other materials, notably mine spoil and fly ash,further confounding identification of its effects. Surprisingly, and in contrast with freshwaterenvironments, even these types of studies are scarce and relate to only a few geographical areas.
Zhang et al. (1995) refer in the abstract of their paper to effects of coal dust on marine organisms,including photosynthetic effects and changes in sediment quality but no details are given (the maintext is in Mandarin). Sampling of sediments around industrialised, coal-mining settlements inSvalbard found elevated concentrations of a range of organic contaminants (Holte et al. 1996).These included PAH, which were assumed to derive from local coal stores via terrestrial runoff.The faunal diversities of these areas were low (based on values of the Shannon-Weaver index), butmuch of this effect was attributed to inputs of fine particulates from glaciers. The variety of sourcesof particulates and chemical contaminants to these environments (coal piles, rubbish dumps,industrial activity, glacial runoff) prevented any clear identification of effects of the presence ofcoal. Paine et al. (1996) observed no reduced species richness of benthic infauna resulting fromthe presence of coal, coke and pitch particles in sediments, in contrast to the generally observedreduction in diversity of biological assemblages along contamination gradients (Pearson & Rosenberg1978, Maurer et al. 1993, Chapman et al. 1996b).
Effects of colliery waste on the northeast coast of England
The most extensive set of studies of effects of coal and colliery waste on benthic assemblages isfrom the coast of northeast England. Colliery waste, together with fly ash from power stations anddredge spoil from the ports of Blyth, Newcastle and Sunderland, has been tipped onto the shoreand dumped off the coast of northeast England since the beginning of the 20th century (Eagle et al.1979). Much of this dumping began before statutory controls were in place to protect the environ-ment and monitoring of the effects of the dumped material did not begin until 1975 (Eagle et al.1979). Dumping of colliery waste at sea has now ceased and only one coastal dumpsite is stilloperating (this operation is licensed as beach nourishment under the coastal defence strategy forthe area; Barnes & Frid 1999). The sea bed along this stretch of coast consists of fine sand indepths of <10 m with gravel and sand among outcrops of rock further offshore (Norton 1985).
The colliery waste consists of ‘minestone’, comprised mainly of sandstones and shales fromwhich coal has been separated by a water-based gravity process, and tailings, which represent thefine fractions of the waste from which coal has been extracted by an oil-water flotation methodand which have a particle size <0.5 mm (Limpenny et al. 1992). Nearly 80% of the waste was<4 mm in diameter at the time of dumping, but the material was abraded by water movement toparticles <1 mm. Colliery waste contains 25–30% coal (determined by loss on combustion: Norton1985, Hyslop et al. 1997). Trace metal concentrations in the colliery waste were generally lowerthan in coal from the same area, suggesting that the coal, rather than the associated minerals, wasthe more important potential source of these contaminants (Eagle et al. 1979, Hyslop et al. 1997).The previously mentioned observation that colliery waste washed up on local beaches containedmuch lower concentrations of trace metals than either the coal or the waste prior to dumpingsuggests that metals from colliery waste may be available to animals and plants living on the seabed in the area where the waste is dumped, and may exert a toxic effect on them. There do notappear to be any measurements of amounts of toxic organic compounds in the waste but these arepresumably also high (Hyslop et al. 1997).
Eagle et al. (1979) examined the effects of colliery and other wastes on the sediments andbenthic organisms at the dumpsites and found that seabed sediments contained >2% of coal along
MICHAEL J. AHRENS & DONALD J. MORRISEY
106
a >11 km stretch of coast. Concentrations of trace metals (particularly Cr, Cu, Ni, Pb and Zn) insediments were high in some areas and corresponded with concentrations of waste. Concentrationsof these metals at some sites exceeded sediment quality guidelines at which biological effects arelikely to occur (Table 6). A later study (Limpenny et al. 1992) reported that concentrations of tracemetals in sediments at the dumpsites were “within the normal range for the north-east coast”, butthis is a region of historical contamination from discharges from heavy industrial and urban areas,in addition to dumping of waste at sea. Concentrations of metals in the sediment offshore frombeach dumpsites only rarely exceeded the sediment quality guidelines at which biological effectswould be expected to occur (Table 6) in the case of Cu, Hg, Pb, Ni and Zn. Limpenny et al. (1992)found more than 50% of coal in sediments around one of the beach disposal sites, and Hyslop et al.(1997) reported 11–27% coal in beach sediments (measured as combustible material after removalof biologically available organic matter with hydrogen peroxide). It must be pointed out, however,that the generally high levels of sediment contamination in this area make it impossible to say thatthe concentrations of contaminants reported were due to the dumping of colliery waste. The bioavail-ability of the contaminants, and the associated probability of toxic effects, is also unknown. Therewas no evidence for accumulation of trace metals by commercially harvested species (various decapodcrustaceans, mussels and finfishes) taken from the inshore zone near the dumpsites (Norton 1985).
Eagle et al. (1979) sampled benthic animals in 1975 and 1976 at two dumpsites, one of whichhad received only colliery waste and small amounts of dredge spoil (i.e., no fly ash). Overall, thesurveys indicated that the effects of dumping on the benthos were limited to the area where thematerial initially settled on the bed. In this region, the benthos was severely depleted in bothabundance and number of species. Effects on surrounding areas could not be shown even thoughthe sediments contained particles of waste as a result of sediment transport by water currents.
Johnson & Frid (1995) and Barnes & Frid (1999) examined recovery of the benthic fauna atsites where dumping colliery waste had ceased. The earlier study compared three former dumpsitesand an undumped control (or reference) site and concluded that the benthic communities were stillperturbed 7.5–12.5 yr after dumping ceased. The number of species was largest at the control site(39 vs. 33–35) but Shannon-Weaver diversity was highest at two of the former dumpsites. Thelatter observation suggested that the level of disturbance caused by dumping favoured diversity,perhaps by preventing competitively dominant species from excluding others. Unfortunately, thisstudy suffered from possible weaknesses of design. These included the fact that there was only onecontrol site, which may have differed from the dumpsites in the nature of its fauna for a variety ofreasons other than the fact that it had not received waste. There was also very limited replicationof sampling because the fauna at each of the study sites was characterised from only three replicategrab samples. Furthermore, sediment transport in the area is in a predominantly north-southdirection, which also corresponds to the relative positions of sites of increasing time since dumpingceased. Consequently, these sites may have continued to receive inputs of colliery and other wasteseven though direct inputs from dumping had ceased.
Barnes & Frid’s (1999) study compared the benthic faunas at six sites, including an activedumpsite, undumped controls and sites that had not been dumped for 3–41 yr. They found differencesin the composition of the fauna between dumped and undumped sites, and an apparent degree ofrecovery at those sites where dumping had ceased, though these differences were not clear-cut.Comparisons of the grain-size distribution and organic-matter content of sediments with the com-position of the faunal communities present suggested that “dumping of colliery spoil was animportant factor determining community composition, rather than the presence of coal per se”. Theauthors also stated, however, that “While influenced by particle size distribution, a greater effectresults from the proportion of coal waste still present… This implies that the greater mobility ofthe lighter coal particles — and the resulting lower stability of the substratum — are responsible
UNBURNT COAL IN THE MARINE ENVIRONMENT
107
for the altered communities”. Differences between the benthic communities at dumped andundumped sites were, therefore, attributed to the destabilising effect of coal particles on thesediment, making it physically less suitable as a habitat for animals, rather than exerting a toxiceffect or smothering resident organisms. Without experimental studies, it is not possible to separatethe first two effects, but the slow recovery of these sites is consistent with the suggestion thatdeposition of material was not the sole cause of observed differences.
In a study of effects of colliery waste on intertidal habitats (as opposed to the subtidal areasstudied by Eagle et al. (1979), Johnson & Frid (1995) and Barnes & Frid (1999)), Hyslop et al.(1997) found that colliery waste had an adverse effect on the number of species present in thelow-shore and mid-shore levels of sandy beaches. A maximum of eight species was found onuncontaminated shores, compared with a maximum of two species on heavily contaminated shores.There were no detectable differences at the high-shore level. Similarly, uncontaminated rocky shorescontained 12–15 species of macroalgae, whereas contaminated shores contained only 5–8. Thediversity of animal communities on rocky shores (measured as the Shannon-Weaver index) was,however, sometimes greater on contaminated shores, although the number of species (usually 7–10)did not differ significantly among shores. Hyslop et al. (1997) concluded that reduced numbers offaunal species on sandy shores were due to decreased stability of the sediment resulting from thepresence of colliery waste, which was made up of larger, more angular particles than the naturalsediment. Concentrations of metals in waste washed up on the shore were much lower than in theunweathered waste. This finding suggested that a large proportion of the metals were leached outof the waste on the sea bed, making it unlikely that the effects on the intertidal fauna were due tothe presence of these toxicants.
One of the species whose abundances correlated inversely with the amount of colliery wastein the sediment was the burrowing, deposit-feeding polychaete Arenicola marina. By comparingthe sediments and the gut contents and faecal material of worms from a heavily coal-contaminatedsite with those from a lightly contaminated site, Hyslop & Davies (1999) found that the worms atthe heavily contaminated site apparently fed selectively on sand grains and rejected coal particles.Selection may have been made on the basis of grain size, and smaller particles of coal were foundin the guts and faeces of worms from both sites. Worms from both sites showed a reluctance toburrow into their native sediment when a 2-mm thick surface layer of colliery waste had beenplaced on the surface, compared with native sediment without the added layer. Despite the rejectionof larger particles (mainly coal) by worms at the more contaminated site, there was no evidenceto suggest that lack of suitable sediment for feeding was the cause of the observed reduction inabundance of A. marina at heavily contaminated sites. Instability of sediments due to the presenceof coal may have been a more important factor.
The species of macroalgae absent from coal-contaminated rocky shores were low-biomass, lessrobust types. Given the fact that toxic effects from coal appeared unlikely, Hyslop et al. (1997)concluded that effects on these species were, therefore, due to abrasion by the suspended particlesof waste in the water. This conclusion was confirmed by laboratory experiments in which theindividuals of the green alga Ulva lactuca exposed for 8 days to colliery waste in containers thatwere shaken to simulate abrasion lost weight relative to controls without waste (Hyslop & Davies1998), as discussed previously. Species with thick, waxy cuticles were not markedly affected bythe presence of waste. The laboratory studies also showed that over 60 days, U. lactuca grew morein the presence of colliery waste in unshaken conditions than in coal-free controls. Hyslop & Davies(1998) suggested that enhanced uptake of inorganic nutrients in the presence of the waste mayhave been responsible for this increased growth and perhaps accounted for the relatively largeabundance of U. lactuca in rock pools at their field sites. No evidence of enhanced uptake wasgiven, however, and possible effects on field populations of algae were not tested experimentally.
MICHAEL J. AHRENS & DONALD J. MORRISEY
108
In summary, the dumping of colliery waste appeared to reduce the species diversity andabundance of intertidal and subtidal assemblages of animals and plants. Although the waste con-tained significant amounts of trace metals, the effects on benthic assemblages were generallyattributed to physical changes (destabilisation) in the sediments and the abrasive action of suspendedparticles of waste. These physical effects were generally localised around the area of input of thecoal. It is important to note that assemblages at dumpsites were compared with nearby controlsthat themselves contained relatively high concentrations of contaminants in their sediments. Anyeffects of this background contamination may have obscured toxic effects of the waste. The factthat the waste contained other materials than coal (sandstones and shales), which also have potentialphysical or chemical effects on biota, confounds interpretation of the observed biological effectsas effects of the coal fraction. Furthermore, the spatial and temporal scales of sampling were limitedin all of the studies reviewed above. None, for example, sampled on more than two occasions, andthe level of spatial replication was generally limited. The naturally large spatial and temporalvariability of benthic assemblages makes it difficult to detect environmental impacts withoutconsiderable spatial and temporal replication, and clear attribution of cause may not be possibleusing the correlative approach in situations where there are multiple sources of impact, such as thecoast of northeast England. Consequently, the apparent absence of clear toxic effects associatedwith coal off the northeast coast of England does not rule out such an effect in areas with lessbackground contamination.
Discussion
Assessment of the marine environmental risks of coal
The general opinion, expressed in many of the studies cited above, is that coal may present aphysical hazard in the marine environment when present in sufficient quantities, but not a chemicalone. The physical effects are largely common to any form of suspended, particulate matter, prin-cipally smothering, abrasion, obstruction and damage to respiratory and feeding organs, and effectsdue to reduction in the quality and quantity of light (Figure 2). Nevertheless, there are some linesof evidence, detailed in preceding sections, supporting the hypothesis that contaminants present incoal can also exert adverse effects on organisms. As with most assessments of risk of adverseecological effects at higher levels of biological organisation caused by contaminant toxicity, aweight-of-evidence approach is essential (Chapman et al. 2002).
The approach chosen in this discussion is a tiered assessment, analogous to those used to assessenvironmental risks associated with, for example, disposal of contaminated sediments at sea (e.g.,the dredge-spoil disposal guidelines given by U.S. EPA/U.S. ACE 1991, 1998, Chevrier & Topping1998, Environment Australia 2002). This type of approach could also be used on a case-by-casebasis in environmental risk assessments for particular types of coal. Rigorous evidence for or againsttoxic effects of the type of coal in question at any tier would obviate the need for testing at subsequenttiers. Where conclusive evidence is not provided by lower tiers, higher-tier testing may be required.
In the first tier, information on the chemical nature of the different types of coal is used toassess the toxic potential of the contaminants present. There is no doubt that such contaminantsare present in all types of coal, as shown by the studies summarised in Tables 2 and 3. For differenttypes of coal, however, the types and combinations of contaminants may vary, together with otherchemical and physical properties, and potential biological effects will therefore also vary. Takingthe coal dumped off the northeast coast of England as an example, where the concentration of coalin the sediments at the dump sites ranged from 2–27% by dry weight, and using the concentrations ofcontaminants in the coal cited by Hyslop et al. (1997), the resulting total concentrations of selectedtrace metals would be Cr 4–50 µg g–1, Cu 5–62 µg g-1, Ni 3.5–44 µg g-1 and Pb 2.4–30 µg g-1.
UNBURNT COAL IN THE MARINE ENVIRONMENT
109
Except for Ni, these values are all below sediment quality guidelines (ANZECC 2000) but inconditions where the proportion of coal in the sediment is larger (say, 50%), other metals wouldalso exceed guideline values. Under these conditions, guidelines for some organic toxicants wouldalso be exceeded for at least some types of coal (see Tables 2 and 3). The critical question, ofcourse, is how bioavailable these contaminants are and under what environmental conditions theyare present. Furthermore, at these concentrations of coal in sediments, physical effects may havemore immediate impact on the biota than any potential toxic effect.
An indication of bioavailability may be provided by information on the quality of runoff fromcoal stockpiles or laboratory-produced leachates, which show that dissolution of potentially toxiccontaminants may occur (see Tables 4 and 5). In an environmental risk assessment for a particulartype of coal, this could be determined using elutriate tests (e.g., U.S. EPA/U.S. ACE 1991) orporewater extracts from coal-contaminated sediments. In risk assessment terms, environmentalconcentrations of the contaminants may be compared with water or sediment quality guidelines,such as those of ANZECC (2000). As a quick-screening test for potentially toxic leachates, it maybe worthwhile to determine leachate pH prior to any comprehensive chemical analysis, becauselow pH, indicative of sulphide oxidation, generally correlates with high concentrations of sulphateand trace metals (Table 4). There is currently little evidence that dissolved PAH concentrations incoal leachates reach levels that exceed water quality guidelines. Coal therefore does not appear tobe a significant source of dissolved PAHs. A critical area of uncertainty in terms of bioavailabilityof contaminants from coal is the degree to which they may be mobilised from particles duringpassage through the guts of animals. This uncertainty applies especially to deposit-feeders butbecause, for example, coal particles were found in the guts of fishes exposed to coal in suspension(Gerhart et al. 1981), other animals might also accumulate contaminants by this route.
The second tier involves assessment of evidence that inorganic and organic contaminants derivedfrom coal may be bioaccumulated. While bioaccumulation does not necessarily indicate an adversebiological effect (Chapman 1997), it does provide unequivocal evidence that the accumulatedcontaminants are present in a bioavailable form. That bioaccumulation of contaminants from coalcan occur is demonstrated by the uptake of Cd by the predatory gastropod Hexaplex trunculus inthe presence of coal particles in the laboratory and field (Siboni et al. 2004). Shaw & Wiggs (1980)suggested that the bivalve Macoma balthica had accumulated hydrocarbons from coal-contaminatedsediments in Alaska (although they did not clearly distinguish ingestion from assimilation). In arisk-assessment context, this tier might involve laboratory studies of animals exposed to coal underenvironmentally realistic conditions and routes of exposure (e.g., deposited or suspended coalparticles), and incorporate comparisons with appropriate reference sediments. Alternatively, it mightfollow defined protocols, such as those in U.S. EPA/U.S. ACE (1991), which include factors toassess when interpreting bioaccumulation values in excess of those in reference sediments. Thesefactors include the phylogenetic diversity of the species in which bioaccumulation occurs, and therange of contaminants that are bioaccumulated. Acute and chronic (steady state) bioaccumulationtests might be included, proceeding from the former to the latter as indicated.
The third tier reviews evidence of biological effects of accumulated contaminants derived fromcoal at the range of levels of biological organisation from the cell to the individual. At one extremeof this continuum, there is evidence that contaminants from coal can have genotoxic effects infishes (Campbell & Devlin 1997). The severity of pneumoconiosis, a respiratory disease prevalentamong coal mine workers caused by quartz particles in coal mine dust, appears to depend not onlyon inorganic coal constituents but also on organic, cytotoxic coal components, such as phenols andcresols, which are readily leachable by biomimetic physiological fluids (Schulz, 1997). At this levelof organisation, it may be reasonable to extrapolate evidence from a range of non-marine to marineorganisms, including the range of toxicological data for effects of coal on humans, if there is reasonto believe that the mechanisms involved are common to both groups.
MICHAEL J. AHRENS & DONALD J. MORRISEY
110
Whereas there are a few documented subcellular effects to coal exposure, current evidencesuggests that coal poses only a subtle toxic hazard, if at all, to biota in the marine environment.The few studies that have observed pronounced toxic effects of coal and coal leachates were carriedout in freshwater environments, where effects related to low pH and high metal concentrationsseemed to dominate. Furthermore, acidity and high metal content affect only a subset of coals,namely sulphur-rich types under oxidising conditions. In the marine environment, pH-related effectsfrom coal are likely to be negligible due to the large buffering capacity of sea water, and elevateddissolved metals concentrations are unlikely to occur due to the much greater dilution and mixingpotential. Dissolved concentrations of organic compounds, such as PAHs, need to be quite high,typically well beyond 10 µg l–1, to exceed toxic thresholds in current water-quality guidelines. Suchconcentrations are unlikely to occur on large scales in the pelagic environment. Thus, toxic effectsto planktonic and nektonic organisms, resulting from dissolved toxicants leached from coal, arenot very likely in the ocean.
There is, however, a greater probability for metals and PAHs to attain toxic threshold concen-trations in pore waters of sediment. The lower exchange rates and limited water volume could allowdissolved compounds to concentrate to high levels before being flushed out, but no measurementsof porewater PAH concentrations of coal-containing sediments have been made. Furthermore,wherever coal occurs in small particle size, there is the potential for ingestion by deposit-feedingbiota. So far, only a few studies have examined toxicity or bioaccumulation of chemical componentsof coal and, from the few cases where ingestion was observed, there is little evidence for pronounceddietary uptake of contaminants. This suggests that the majority of metals and hydrocarbons con-tained in coal are, indeed, present in forms unable to pass through the gut membranes or otherepithelia. Digestive bioavailability is likely to be related to the digestive chemistry of the ingestingorganism and will depend on factors such as enzyme activity, surfactant concentration and dissolvedorganic carbon concentration. However, even organisms with relatively aggressive gut conditions,such as mammals or deposit-feeding polychaetes, seem to leach only very small amounts of toxiccompounds from coal.
The fourth tier of evidence concerns alterations to populations and assemblages of organismsin situ. Here, however, there is very little suitable evidence available at present. Evidence of chemicaleffects from existing studies, such as those of the northeast coast of England, are confounded bythe presence of stressors other than unburnt coal, and by physical effects of the coal itself.
In summary, while the presence of a wide variety of contaminants in most types of coal givescause for concern, in many situations their low aqueous extractability and bioavailability appearsto safeguard against toxic effects. Nevertheless, under certain circumstances and with some typesof coal, leaching of toxic components has been demonstrated and these may be of greater biologicalsignificance. In addition, very little is known about the effects of ingestion and digestion ofparticulate coal on the solubility of contaminants. This uncertainty concerning the toxicologicaleffects of coal is in contrast to the demonstrable physical effects. In many cases, the toxic effects mayaffect biota at lower environmental concentrations of coal than those at which physical effectsmight become apparent. In many situations requiring an assessment of potential effects of coal, allof these factors may need to be considered in a weight-of-evidence approach.
Mitigating environmental risks from coal
This brief overview is intended only to provide a context for the discussion of marine environmentalrisks from coal. It is not intended to be exhaustive and certainly does not pretend to any specialistknowledge of the environmental management of coal handling facilities.
The principal sources of unburnt coal to marine environments are the preparation of coal toremove impurities (involving various washing and flotation techniques), disposal of mine wastes
UNBURNT COAL IN THE MARINE ENVIRONMENT
111
at sea and the storage and transport of coal, particularly at ports (Figure 1). This coal contaminationmay enter the marine environment directly, as in the case of coastal coal preparation plants orloading and unloading at sea ports, or via rivers and estuaries. The efficiency of separation andrecovery of coal from mine wastes is likely to have been optimised for economic reasons (i.e.,minimising wastage of coal). In terms of potentially large, direct inputs to marine environments,losses during storage and transport probably offer the greatest scope for cost-effective mitigation.
Mechanisms of contamination during storage and loading/unloading include runoff from storageand handling areas, airborne transport of dust from stockpiles, slumping and collapse of stockpilesduring rainfall, spillage from conveyor belts carrying coal to and from storage areas and spillage atthe point of transfer from conveyor to ship or vice versa (Sydor & Stortz 1980). The scale and relativeimportance of these inputs will depend on factors such as the design of the loading and storagefacilities, local climate and the volume and type of coal handled. Appropriate mitigation measureswill, therefore, often be site-specific and many modern coal-handling facilities will have environ-mental management systems in place to assess and manage these environmental risks. Generalmethods of mitigating inputs of coal and leachates to the marine environment are discussed in thefollowing paragraphs.
Contamination from wind-blown coal dust can be considerable. Sydor & Stortz (1980) estimatedthat 20 t of dust entered Lake Superior each year from a coal shipment facility, 4 t being depositedafter winter ice melted. Mitigation of inputs of dust to the environment is achieved by: reducingthe amount of time that coal spends in storage areas; covering storage areas (often impractical forlarge areas); ensuring adequate water content at unloading areas; damping of stockpiles and transferpoints with water; managing the stockpiling machinery to minimise the exposure of coal to windsduring operation (e.g., maintaining minimal height of stacking booms); compacting of coal instockpiles; managing stockpile height to minimise exposure to wind, particularly at times of yearwhen strong winds are prevalent; using weather forecast information to respond to predicted adverseweather conditions; cleaning up spillages regularly; and using real-time dust monitoring data toreactively manage dust controls (Ports Corporation of Queensland 2002, World Coal Institute 2004).Sydor & Stortz (1980) observed that dumping of coal from an overhead conveyor generated lessdust and caused less down-wind deposition than did grooming operations on stockpiles by caterpillartractors. Water is also used to suppress dust at transfer points between conveyors and ships, andelevated conveyors and transfer areas can be enclosed to minimise the exposure of coal to winds.In addition to reducing dust generation, enclosing conveyors will also reduce spillage of coal dueto vibration and overflow at points where coal is transferred from one conveyor to another.
Use of water to suppress dust adds to rainfall runoff as a mechanism for the generation ofleachates from stockpiles. Stockpile areas can be bunded to control runoff and prevent it fromentering natural waterways. Runoff can then be directed through drainage systems fitted with sumpsand settling ponds to reduce the amount of particulate coal in suspension (Ports Corporation ofQueensland 2002, World Coal Institute 2004). Removal of particulates will help trap the majorityof PAHs and trace metals before reaching the marine environment. Design of bunds and drainagesystems has to take into account the volume of coal to be stored in the future (which affects thevolume of the bunded area available for water retention) and the intensity and duration of localrainfall. The quality of the leachate once particulates have settled out will depend very strongly onchemical and physical characteristics of the coals, as discussed above. This, in turn, will determinethe level of treatment required before runoff is allowed to enter local waterways or the sea. Wateris likely to be recycled for use in dust suppression for environmental and economic reasons (PortsCorporation of Queensland 2002, World Coal Institute 2004). This may increase concentrations ofdissolved contaminants over time and lead to potentially more severe environmental effects if runoffaccidentally enters natural waterways due, for example, to overflows during intense rainfall, orincrease the level of treatment required before intentional discharge. Because concentrations of
MICHAEL J. AHRENS & DONALD J. MORRISEY
112
contaminants tend to be highest in the ‘first flush’ of leachate from coal stockpiles during rainfallevents (Davis & Boegly 1981a), it may be possible to divert and treat only this component.
Another option, especially for long-term storage, is to treat the coal pile with surfactants andwater-repellent compounds that hinder the entry of water into the pile. Cationic surfactants aregenerally favoured because of their superior wetting ability (Tien & Kim 1997). While surfactantsperform well in reducing dust levels, it is conceivable, albeit speculative, that they negatively affectleachate quality by enhancing solubilisation of particle-bound contaminants. The drawbacks ofsealing surfaces of storage piles are that the geotechnical properties of the coal are changed andthat the coal becomes more difficult to excavate and process. A third option, aimed at minimisingthe generation of acid leachates and increased metal concentrations in runoff from sulphur-richcoal piles, is to prevent or counteract the oxidation of pyrite and other sulphur-containing com-pounds by bacteria. One successful approach is to promote the growth of sulphate-reducing bacteriain coal piles (Kim et al. 1999), which has been shown to neutralise acids and reduce dissolvedconcentrations by 99% for Cd, Cu and Zn, and 87% for Ni. Addition of caustic soda (NaOH) toleachates to neutralise acids is common practice, and it has been suggested that the deliberatestorage of different types of coals conjointly (e.g., sulphur-poor coal downstream of sulphur-richcoal) might help neutralise or ameliorate adverse leachate properties (Coward et al. 1978).
Slumping of stockpiles is caused by saturation of the piles with water, for example duringheavy rain. The risk of slumping varies with the type of coal and its existing water content. It canbe minimised by covering and compacting the stockpile, minimising its height and providingdrainage underneath it. Bunding of stockpile areas is used to contain slumps if they do occur.Location of stockpiles as far as practical from the water line will reduce impacts from wind-blowndust and slumping.
Directions for future research
Bioavailability of contaminants from coal
From the foregoing sections it is clear that coal is a heterogeneous mineral whose chemicalproperties are highly variable. This means that, unlike studies of its physical effects, which relateprimarily to particle size, density and concentrations, it is impossible to define a ‘representative’coal sample from a chemical standpoint. Thus, even though some studies have suggested lowbioavailability of toxic compounds for a number of coal samples, these data are not sufficient toreject the hypothesis that some coals are toxic to aquatic organisms. If one adopts the precautionaryprinciple, any coal sample that is known to contain high concentrations of metals and organiccompounds is potentially capable of releasing these to the environment. Leaching studies andbioassays are required to prove otherwise.
It may be safe to say that wherever particulate coal is present in the aquatic environment, effectsfrom increased suspended solids concentrations and modified benthic substrata are likely to dom-inate over toxic chemical effects. For this reason, it is recommended that any studies on chemicaltoxic effects of coal should begin with particle-free (i.e., filtered or centrifuged) leachates of coal.This approach would avoid confounding toxic effects with physical effects. The procedures forpreparing a leachate whose properties are representative of those encountered during coal pilestorage or upon deposition of coal into the aquatic environment will depend on local conditionsand need to be carefully evaluated. For example, if coal dust is ultimately discharged into themarine environment and toxic effects of this discharge are to be evaluated, leaching studies needto be conducted with sea water rather than freshwater or distilled water. To investigate whethertoxic compounds in coal particles may be assimilated by ingestion, biomimetic leaching experimentsthat simulate the conditions in the digestive tract of organisms might be useful. Such experiments
UNBURNT COAL IN THE MARINE ENVIRONMENT
113
would provide a rapid estimate of the potentially bioavailable fraction of coal contaminants. Finally,more careful bioassays with marine organisms are needed to provide a convincing case that toxiceffects from coal are negligible.
To help comparisons with previous and future studies, as many characteristics of the unburntcoal sample as possible should be recorded, such as rank, sulphur content, leaching duration, solid-to-liquid ratio in the raw, unfiltered leachate, and particle size. These variables greatly affect leachateproperties and concentrations of some potential toxicants (e.g., metals). What is currently lackingis a comprehensive ecotoxicological comparison of different coal types and their leachates. A betterknowledge of which types of coals have the potential to generate toxicity is central to effective,scientifically based mitigation of adverse effects.
Manipulative laboratory and field experiments
As discussed above, there are several missing links in the process of environmental risk assessmentfor coal. Furthermore, where coal is present in the marine environment, any potential ecotoxico-logical effects it may have are likely to be overwhelmed or confounded by more obvious physicaleffects, or by chemical effects of contaminants from other sources. Addressing these issues requiresmanipulative experiments in the laboratory and field to determine the bioavailability of coal-derivedtoxicants and to identify unambiguously their effects without the presence of confounding orobscuring factors. Field studies, including in situ toxicity testing and studies involving spiking coalinto uncontaminated sediments, should be possible even at relatively large spatial scales because ofcoal’s ease of handling. These studies could be extended to compare various types of coal, differentdegrees of weathering and particle size, and other factors that influence the toxic potential of coal.
Long-term monitoring and correlational studies
If, as predicted, demand for coal continues to grow, and new exporting and importing facilities areconstructed, opportunities may arise for before-after/control-impact (BACI) studies of the effectsof coal terminals on the surrounding environment. These studies would include monitoring of coalcontamination, and any associated changes in the environmental concentrations of coal-derivedcontaminants (including those that are characteristic of coal and would allow clear identificationof the source) and the health status of resident biota. They would include appropriately located andreplicated control locations and would continue for a sufficient time before and after the start ofcoal-transporting operations for an adequate assessment of background temporal variation in theenvironment and its biota, and for any effects (physical and chemical) to emerge. Estimates ofthe time required for effects to emerge might be based on modelling of environmental input andfate of coal (e.g., Biggs et al. 1984) and of ecological responses (see, e.g., the discussion ofmodelling of effects of sedimentation on rocky-shore organisms in Airoldi 2003), and the resultsof manipulative experiments, such as those described above. Ideally, such studies would take placein the absence of other sources of impact, such as industrial discharges or spoil grounds, whichmight confound or obscure any effects of coal.
Needless to say, the above requirements are unlikely to be fulfilled in many situations. Mostexpansions of coal-transporting facilities are likely to occur by enlargement of existing ports ratherthan construction of new ones. In this situation, the environment is likely to be affected already,particularly at older ports where past environmental management practices were less strict thanthey often are today. Exceptions may occur where new coalfields are developed in areas whereland transport infrastructure does not exist to allow transfer to an existing port, or expansion mayinvolve construction of an additional terminal sufficiently far away from existing ones that it lies
MICHAEL J. AHRENS & DONALD J. MORRISEY
114
outside the field of effects. Such opportunities should be seized in order to minimise possibleenvironmental effects and to advance our understanding of them. In practice, however, the percep-tion, right or wrong, that coal is generally a low-risk contaminant in the marine environment seemsto lead to the perception that such studies are not cost effective.
Conclusions
Despite coal’s long and often conspicuous presence as a natural and anthropogenic contaminant inmarine environments, its toxicological effects have received surprisingly little attention. As we haveseen, this stems at least partly from a perception that the bioavailability of contaminants in coal isvery limited and that at levels of coal contamination at which estimates of bioavailable concentra-tions of contaminants might give cause for concern, acute physical effects are likely to be muchmore significant. However, we have also seen that the very variable chemical properties of coal,and the environment in which it occurs, may give rise to circumstances in which contaminantmobility and bioavailability is enhanced. Understanding the mechanisms controlling bioavailabilityis probably the key to predicting and mitigating environmental effects of coal. It is a field thatoffers wide scope for experimental studies, as does investigation of biological responses to coal,particularly at higher levels of biological organisation.
Acknowledgements
We are very grateful to John Bankson (U.S. EPA, Duluth, Minnesota), Bob Brunner (Ports Corpo-ration of Queensland), Peter Chapman (EVS Environment Consultants) and Chris Frid (Universityof Newcastle-Upon-Tyne) for providing information and advice on coal effects and their manage-ment; to Peter Chapman and Craig Depree (NIWA) for helpful comments on an earlier draft ofthis review and to Robin Gibson for excellent editorial support; to Wayne Barnett (Port MarlboroughNew Zealand Ltd) for the original invitation to prepare an assessment of effects of coal in themarine environment; and to the NIWA library staff, particularly Joke Baars, for tracking downnumerous papers and reports. Nevertheless, any errors, omissions or misinterpretations containedin this work remain our own responsibility. Finally, given the breadth of the published and unpub-lished international literature on coal properties and its environmental effects, we wish to extendour apologies to any authors whose contributions may have been omitted in this review.
References
Adam, P. 2002. Saltmarshes in a time of change. Environmental Conservation 29, 39–61.Airoldi, L. 2003. The effects of sedimentation on rocky coast assemblages. Oceanography and Marine Biology:
An Annual Review, 41, 161–236.Allen, J.R.L. 1987. Coal dust in the Severn Estuary, southwestern UK. Marine Pollution Bulletin 18, 169–174.Alpern, B. 1977. Evaluation of the energy potential of carbonaceous sediments. World Coal 3, 17–20.Anderson, W.C. & Youngstrom, M.P. 1976. Coal pile leachate — quantity and quality characteristics. Journal
of the Environmental Engineering Division, 102, 1239–1253.Andersson, M. 1988. Toxicity and tolerance of aluminium in vascular plants. Water Air and Soil Pollution 39,
439–462.ANZECC 2000. Australian and New Zealand guidelines for fresh and marine water quality. National water
quality management strategy. Wellington and Canberra: Australian and New Zealand Environmentand Conservation Council and Agriculture and Resource Management Council of Australia and NewZealand. Online. Available HTTP: http://www.mfe.govt.nz/publications/water/anzecc-water-quality-guide-02/index.html (accessed 30 June 2004).
UNBURNT COAL IN THE MARINE ENVIRONMENT
115
Auld, A.H. & Schubel, J.R. 1978. Effects of suspended sediment on fish eggs and larvae: a laboratoryassessment. Estuarine and Coastal Marine Science 6, 153–164.
Australian Coal Association 2004. Black coal exports from Australia. Australian Coal Association. Online.Available HTTP: http://www.australiancoal.com.au (accessed 30 June 2004).
Bach, S.S., Borum, J., Fortes, M.D. & Duarte, C.M. 1998. Species composition and plant preference of mixedseagrass beds along a siltation gradient at Cape Bolinao, The Philippines. Marine Ecology ProgressSeries 174, 247–256.
Barnes, N. & Frid, C.L.J. 1999. Restoring shores impacted by colliery spoil dumping. Aquatic Conservation:Marine and Freshwater Ecosystems 9, 75–82.
Barrick, R.C., Furlong, E.T. & Carpenter, R. 1984. Hydrocarbon and azaarene markers of coal transport toaquatic sediments. Environmental Science and Technology 18, 846–853.
Barrick, R.C. & Prahl, F.G. 1987. Hydrocarbon geochemistry of the Puget Sound region: III. Polycyclicaromatic hydrocarbons in sediments. Estuarine Coastal and Shelf Science 25, 175–191.
Bayne, B.L. & Hawkins, A.J.S. 1992. Ecological and physiological aspects of herbivory in benthic suspension-feeding molluscs. In Plant-Animal Interactions in the Marine Benthos, S.J. Hawkins et al. (eds).Oxford: Clarendon Press, 265–288.
Bender, M.E., Roberts, M.H. & de Fur, P.O. 1987. Unavailability of polynuclear aromatic hydrocarbons fromcoal particles to the eastern oyster. Environmental Pollution 44, 243–260.
Biggs, R.B., Sharp, J.H., Frake, A.C., Pike, S.E., Manus, A.T., Cronin, J.H. & Wypyszinski, A.W. 1984.Environmental effects and regulatory options of coal transfer operations in lower Delaware Bay. Dover,Delaware, U.S.: State of Delaware Department of Natural Resources and Environmental Control.
Birch, G., Ingleton, T. & Taylor, S. 1997. Environmental implications of dredging in the world’s second largestcoal exporting harbour, Port Hunter, Australia. Journal of Marine Environmental Engineering 4,133–145.
Blackmore, G. & Wang, W.X. 2004. The transfer of cadmium, mercury, methylmercury, and zinc in an intertidalrocky shore food chain. Journal of Experimental Marine Biology and Ecology 307, 91–110.
Boehm, P.D., Page, D.S., Burns, W.A., Bence, A.E., Mankiewicz, P.J. & Brown, J.S. 2001. Resolving theorigin of the petrogenic hydrocarbon background in Prince William Sound, Alaska. EnvironmentalScience and Technology 35, 471–479.
Brady, N.C. & Weill, R.R. 2002. The Nature and Properties of Soils. 13th edition. Englewood Cliffs: PrenticeHall.
Briggs, K.B., Richardson, M.D. & Young, D.K. 1996. The classification and structure of megafaunal assem-blages in the Venezuela Basin, Caribbean Sea. Journal of Marine Research 54, 705–730.
Bucheli, T.D. & Gustafsson, O. 2000. Quantification of the soot-water distribution coefficient of PAHs providesmechanistic basis for enhanced sorption observations. Environmental Science and Technology 34,5144–5151.
Buchman, M.F. 1999. NOAA screening quick reference tables. Seattle, U.S.: Coastal Protection and Resto-ration Division, National Oceanographic and Atmospheric Administration.
Campbell, P.M. & Devlin, R.H. 1997. Increased CYP1A1 and ribosomal protein L5 gene expression in ateleost: the response of juvenile chinook salmon to coal dust exposure. Aquatic Toxicology 38, 1–15.
Carlson, C.A. 1990. Subsurface leachate migration from a reject coal pile in South Carolina. Water Air andSoil Pollution 53, 345–366.
Carlson, C.L. & Carlson, C.A. 1994. Impacts of coal pile leachate on a forested wetland in South Carolina.Water Air and Soil Pollution 72, 89–109.
Carlson, R.M., Oyler, A.R., Gerhart, E.H., Caple, R., Welch, K.J., Kopperman, H.L., Bodenner, D. & Swanson,D. 1979. Implications to the aquatic environment of polynuclear aromatic hydrocarbons liberatedfrom Great Plains coal. Duluth, U.S.: United States Environmental Protection Agency Report No.EPA-600/3-79-093.
Carlton, J.T. 1985. Transoceanic and interoceanic dispersal of coastal marine organisms: the biology of ballastwater. Oceanography and Marine Biology: An Annual Review 23, 313–371.
Carlton, J.T. 1996. Pattern, process, and prediction in marine invasion ecology. Biological Conservation 78,97–106.
Chapman, P.M. 1997. Is bioaccumulation useful for predicting impacts? Marine Pollution Bulletin 34, 282–283.
MICHAEL J. AHRENS & DONALD J. MORRISEY
116
Chapman, P.M. 2004. Indirect effects of contaminants. Marine Pollution Bulletin 48, 411–412.Chapman, P.M., Downie, J., Maynard, A. & Taylor, L.A. 1996a. Coal and deodorizer residues in marine
sediments — contaminants or pollutants? Environmental Toxicology and Chemistry 15, 638–642.Chapman, P.M., McDonald, B.G. & Lawrence, G.S. 2002. Weight-of-evidence issues and frameworks for
sediment quality (and other) assessments. Human and Ecological Risk Assessment 8, 1489–1515.Chapman, P.M., Paine, M.D., Arthur, A.D. & Taylor, L.A. 1996b. A triad study of sediment quality associated
with a major, relatively untreated marine sewage discharge. Marine Pollution Bulletin 32, 47–64.Chapman, P.M. & Wang, F. 2001. Assessing sediment contamination in estuaries. Environmental Toxicology
and Chemistry 20, 3–22.Cheam, V., Reynoldson, T., Garbai, G., Rajkumar, J. & Milani, D. 2000. Local impacts of coal mines and
power plants across Canada. II. Metals, organics and toxicity in sediments. Water Quality ResearchJournal of Canada 35, 609–631.
Chevrier, A. & Topping, P.A. 1998. National guidelines for monitoring dredged and excavated materials atocean disposal sites. Quebec, Canada: Environment Canada, Marine Environment Division.
Coalportal 2004. Production and Trade. Sydney: Barlow Jonkers Pty Ltd. Online. Available HTTP:http://www.coalportal.com (accessed 30 June 2004).
Cook, A.M. & Fritz, S.J. 2002. Environmental impacts of acid leachate derived from coal-storage piles upongroundwater. Water Air and Soil Pollution 135, 371–388.
Coward, N.A., Horton, J.W., Koch, R.G. & Morden, R.D. 1978. Static coal storage — biological and chemicaleffects on the aquatic environment. Duluth, U.S.: United States Environmental Protection Agency.Report No. EPA 600/3-80-083.
Cox, D.B., Chu, T.Y.J. & Ruane, R.J. 1977. Quality and treatment of coal pile runoff. In Proceedings of theThird Symposium on Coal Preparation, October 1977. National Coal Association and BituminousCoal Research, (cited in Davies & Boegly 1981a, no further information given).
Curran, K.J., Irvine, K.N., Droppo, I.G. & Murphy, T.P. 2000. Suspended solids, trace metal and PAHconcentrations and loadings from coal pile runoff to Hamilton Harbour, Ontario. Journal of GreatLakes Research 26, 18–30.
Daly, M.A. & Mathieson, A.C. 1977. The effects of sand movement on intertidal seaweeds and selectedinvertebrates at Bound Rock, New Hampshire, USA. Marine Biology 43, 45–55.
Davies-Colley, R. & Smith, D. 2001. Turbidity, suspended sediment, and water clarity: a review. Journal ofthe American Water Resources Association 37, 1085–1102.
Davis, E.C. & Boegly, W.J.J. 1981a. A review of water quality issues associated with coal storage. Journalof Environmental Quality 10, 127–133.
Davis, E.C. & Boegly, W.J.J. 1981b. Coal pile leachate quality. Journal of the Environmental EngineeringDivision 107, 399–417.
Ding, Z., Zheng, B., Long, J., Belkin, H.E., Finkelman, R.B., Chen, C., Zhou, D. & Zhou, Y. 2001. Geologicaland geochemical characteristics of high arsenic coals from endemic arsenosis areas in southwesternGuizhou Province, China. Applied Geochemistry 16, 1353–1360.
Di Toro, D.M. & McGrath, J.A. 2000. Technical basis for narcotic chemicals and polycyclic aromatichydrocarbon criteria. II. Mixtures and sediments. Environmental Toxicology and Chemistry 19,1971–1982.
Di Toro, D.M., McGrath, J.A. & Hansen, D.J. 2000. Technical basis for narcotic chemicals and polycyclicaromatic hydrocarbon criteria. I. Water and tissue. Environmental Toxicology and Chemistry 19,1951–1970.
Duarte, C.M. 1991. Seagrass depth limits. Aquatic Botany 40, 363–377.Duarte, C.M., Terrados, J., Agawin, N.S.R., Fortes, M.D., Bach, S. & Kenworthy, W.J. 1997. Response of a
mixed Philippine seagrass meadow to experimental burial. Marine Ecology Progress Series 147,285–294.
Duedall, I.W., Humphries, E.M., Heaton, M.G., Oakley, S.A. & Wilke, R.J. 1982. Stabilized coal waste in theChesapeake Bay-Choptank River Estuary: Environmental investigations. Stony Brook, U.S.: StateUniversity of New York, Marine Sciences Research Center.
Duedall, I.W., Kester, D.R., Park, P.K. & Ketchum, B.H. (eds). 1985a. Wastes in the Ocean. Volume 4. EnergyWastes in the Ocean. New York: John Wiley & Sons.
UNBURNT COAL IN THE MARINE ENVIRONMENT
117
Duedall, I.W., Ketchum, B.H., Park, P.K. & Kester, D.R. (eds). 1985b. Wastes in the Ocean. Volume 1. Industrialand Sewage Wastes in the Ocean. New York: John Wiley & Sons.
Eadie, B.J., Faust, W., Gardner, W.S. & Nalepa, T.F. 1982. Polycyclic aromatic hydrocarbons in sedimentsand associated benthos in Lake Erie. Chemosphere 11, 185–191.
Eagle, R.A., Hardiman, P.A., Norton, M.G., Nunny, R.S. & Rolfe, M.S. 1979. The field assessment of effectsof dumping wastes at sea. 5. The disposal of solid wastes off the north-east coast of England. Lowestoft,U.K.: Ministry of Agriculture, Fisheries and Food, Directorate of Fisheries Research.
Emerson, S.E. & Zedler, J.B. 1978. Recolonization of intertidal algae: an experimental study. Marine Biology44, 315–324.
Environment Australia. 2002. National ocean disposal guidelines for dredged material. Canberra: EnvironmentAustralia.
Environment Canada. 2002. Canadian Water Quality Guidelines. Ottawa: Environment Canada. Online. Avail-able HTTP: http://www.ec.gc.ca/ceqg-rcqe/English/Ceqg/Water/default/cfm (accessed 30 June 2004).
Esselink, P., Dijkema, K.S., Reents, S. & Hageman, G. 1998. Vertical accretion and profile changes inabandoned man-made tidal marshes in the Dollard estuary, the Netherlands. Journal of CoastalResearch 14, 570–582.
Evangelou, V.P. 1995. Pyrite Oxidation and Its Control. Boca Raton, Florida: CRC Press.Fahey, B.D. & Coker, R.J. 1992. Sediment production from forest roads in Queen Charlotte Forest and potential
impact on marine water quality, Marlborough Sounds, New Zealand. New Zealand Journal of Marineand Freshwater Research 26, 187–195.
Featherby, S.F. & Dodd, D.J.R. 1977. Control of air and water contaminants from coal piles. Presented at ASCEConference, Dallas, Texas. (Cited in Davis & Boegly 1981b, Swift 1985, no further information given.)
Fendinger, N.J., Radway, J.C., Tuttle, J.H. & Means, J.C. 1989. Characterization of organic material leachedfrom coal by simulated rainfall. Environmental Science and Technology 23, 170–177.
Ferrini, V.L. & Flood, R.D. 2001. Sedimentary characteristics and acoustic detectability of ship-deriveddeposits in western Lake Ontario. Journal of Great Lakes Research 27, 210–219.
Foa, V., Elia, G., Schiavulli, N., Sartorelli, P., Schiarra, G., Cenni, A., Novelli, M.T., Mangani, F., Cecchetti,G. & Iachetta, R. 1998. The non-bioavailability of carcinogenic polycyclic aromatic hydrocarbonscontained in coal dust. La Medicina del Lavoro 89, 68–77.
Francis, W. 1961. Coal — Its Formation and Composition. London: Edward Arnold.French, P.W. 1993a. Areal distribution of selected pollutants in contemporary intertidal sediments of the Severn
Estuary and Bristol Channel, UK. Marine Pollution Bulletin 27, 692–697.French, P.W. 1993b. Post-industrial pollutant levels in contemporary Severn Estuary intertidal sediments,
compared to pre-industrial levels. Marine Pollution Bulletin 26, 30–35.French, P.W. 1993c. Seasonal and inter-annual variation of selected pollutants in modern intertidal sediments,
Aust Cliff, Severn Estuary. Estuarine Coastal and Shelf Science 37, 213–219.French, P.W. 1998. The impact of coal production on the sediment record of the Severn Estuary. Environmental
Pollution 103, 37–43.Geller, W., Klapper, H. & Salomons, W. (eds). 2002. Acidic Mining Lakes: Acid Mine Drainage, Limnology
and Reclamation. Berlin: Springer-Verlag.Gerhardt, A. 1993. Review of impact of heavy metals on stream invertebrates with special emphasis on acid
conditions. Water Air and Soil Pollution 66, 289–314.Gerhart, D.Z., Richter, J.E., Curran, S.J. & Robertson, T.E. 1980. Algal bioassays with leachates and distillates
from western coal. Duluth, U.S.: United States Environmental Protection Agency, Report No. EPA-600/3-79-093.
Gerhart, E.H., Liukkonen, R.J., Carlson, R.M., Stokes, G.N., Lukasewycz, M.T. & Oyler, A.R. 1981. Histo-logical effects and bioaccumulation potential of coal particulate-bound phenanthrene in the fatheadminnow Pimephales promelas. Environmental Pollution Series A 25, 165–180.
Ghosh, U., Gillette, J.S., Luthy, R.G. & Zare, R.N. 2000. Microscale location, characterization, and associationof polycyclic aromatic hydrocarbons on harbor sediment particles. Environmental Science and Tech-nology 34, 1729–1736.
Ghosh, U., Talley, J.W. & Luthy, R.G. 2001. Particle-scale investigation of PAH desorption kinetics andthermodynamics from sediment. Environmental Science and Technology 35, 3468–3475.
MICHAEL J. AHRENS & DONALD J. MORRISEY
118
Gluskoter, H.J., Ruch, R.R., Miller, W.G., Cahill, R.A., Dreher, G.B. & Kuhn, J.K. 1977. Trace elements incoal: occurrence and distribution. Illinois State Geological Survey, Circular No. 499.
Goldberg, E.D., Gamble, E., Griffin, J.J. & Koide, M. 1977. Pollution history of Narragansett Bay as recordedin its sediments. Estuarine and Coastal Marine Science 5, 549–561.
Goldberg, E.D., Hodge, V., Koide, M., Griffin, J.J., Gamble, E., Bricker, O.P., Matisoff, G., Holdren Jr, G.R.& Braun, R. 1978. A pollution history of Chesapeake Bay. Geochimica et Cosmochimica Acta 42,1413–1425.
Griffin, J.J. & Goldberg, E.D. 1979. Morphologies and origin of elemental carbon in the environment. Science206, 563–565.
Hainly, R.A., Reed, L.A., Flippo, H.N. & Barton, G.J. 1995. Deposition and simulation of sediment transportin the lower Susquehanna River reservoir system. United States Geological Survey Water-ResourcesInvestigations Report 95-4122.
Hall Jr, L.W. & Anderson, R.D. 1995. The influence of salinity on the toxicity of various classes of chemicalsto aquatic biota. Critical Reviews in Toxicology 25, 281–346.
Hall Jr, L.W. & Burton, D.T. 1982. Effects of power plant coal pile and coal waste runoff and leachate onaquatic biota: an overview with research recommendations. Critical Reviews in Toxicology 10, 287–302.
Hedvall, R. & Erlandsson, B. 1996. Radioactivity concentrations in non-nuclear industries. Journal of Envi-ronmental Radioactivity 32, 19–31.
Herbert, D.W.M. & Richards, J.M. 1963. The growth and survival of fish in some suspensions of solids ofindustrial origin. International Journal of Air and Water Pollution 7, 297–302.
Hillaby, B.A. 1981. The effects of coal dust on ventilation and oxygen consumption in the Dungeness crab,Cancer magister. Canadian Technical Report of Fisheries and Aquatic Sciences No. 1033, 1–18.
Holte, B., Dahle, S., Gulliksen, B. & Naes, K. 1996. Some macrofaunal effects of local pollution and glacier-induced sedimentation, with indicative chemical analyses, in the sediments of two Arctic fjords. PolarBiology 16, 549–557.
Hughes, G.M. 1975. Coughing in the rainbow trout (Salmo gairdneri) and the influence of pollutants. RevueSuisse de Zoologie 82, 47–64.
Hyslop, B.T. & Davies M.S. 1998. Evidence for abrasion and enhanced growth of Ulva lactuca L. in thepresence of colliery waste particles. Environmental Pollution 101, 117–121.
Hyslop, B.T. & Davies, M.S. 1999. The effect of colliery waste on the feeding of the lugworm Arenicolamarina. Journal of Sea Research 42, 147–155.
Hyslop, B.T., Davies, M.S., Arthur, W., Gazey, N.J. & Holroyd, S. 1997. Effects of colliery waste on littoralcommunities in north-east England. Environmental Pollution 96, 383–400.
Johnson, L.J. & Frid, C.L.J. 1995. The recovery of benthic communities along the County Durham coast aftercessation of colliery spoil dumping. Marine Pollution Bulletin 30, 215–220.
Kendrick, G.A. 1991. Recruitment of coralline crusts and filamentous turf algae in the Galapagos archipelago:effect of simulated scour, erosion and accretion. Journal of Experimental Marine Biology and Ecology147, 47–63.
Kim, S.D., Kilbane, J.J. II & Cha, D.K. 1999. Prevention of acid mine drainage by sulfate reducing bacteria:organic substrate addition to mine waste piles. Environmental Engineering Science 16, 139–146.
Lake, R.G. & Hinch, S.G. 1999. Acute effects of suspended sediment angularity on juvenile coho salmon(Oncorhynchus kisutch). Canadian Journal of Fisheries and Aquatic Sciences 56, 862–867.
Latimer, J.S. & Zheng, J. 2003. The sources, transport and fate of PAHs in the marine environment. In PAHs:An Ecotoxicological Perspective, P. Douben, (ed.), Chichester: Wiley, 9–33.
Leppard, G.G., Flannigan, D.T., Mavrocordatos, D., Marvin, C.H., Bryant, D.W. & McCarry, B.E. 1998.Binding of polycyclic aromatic hydrocarbons by size classes of particulate in Hamilton Harbor water.Environmental Science and Technology 32, 3633–3639.
Limpenny, D.S., Rowlatt, S.M. & Manning, P.M. 1992. Environmental impact of marine colliery waste disposaloperations on the sea bed off Seaham, County Durham. Lowestoft, U.K.: Ministry of Agriculture,Fisheries and Food, Directorate of Fisheries Research.
Littler, M.M., Martz, D.R. & Littler, D.S. 1983. Effects of recurrent sand deposition on rocky intertidalorganisms: importance of substrate heterogeneity in a fluctuating environment. Marine EcologyProgress Series 11, 129–139.
UNBURNT COAL IN THE MARINE ENVIRONMENT
119
Long, E.R., MacDonald, D.D., Smith, S.L. & Calder, F.D. 1995. Incidence of adverse biological effects withinranges of chemical concentrations in marine and estuarine sediments. Environmental Management19, 81–97.
Longstaff, B.J. & Dennison, W.C. 1999. Seagrass survival during pulsed turbidity events: the effects of lightdeprivation on the seagrasses Halophila pinifolia and Halophila ovalis. Aquatic Botany 65, 105–121.
Marbà, N. & Duarte, C.M. 1994. Growth response of the seagrass Cymodocea nodosa to experimental burialand erosion. Marine Ecology Progress Series 107, 307–311.
Maurer, D., Keck, R.T., Tinsman, J.C., Leathem, W.A., Wethe, C., Lord, C. & Church, T.M. 1986. Verticalmigration and mortality of marine benthos in dredged material: a synthesis. Internationale Revue derGesamten Hydrobiologie 71, 49–63.
Maurer, D., Robertson, G. & Gerlinger, T. 1993. San Pedro Shelf California: Testing the Pearson-RosenbergModel (PRM). Marine Environmental Research 35, 303–321.
Mayer, L.M., Chen, Z., Findlay, R.H., Fang, J.S., Sampson, S., Self, R.F.L., Jumars, P.A., Quetel, C. & Donard,O.F.X. 1996. Bioavailability of sedimentary contaminants subject to deposit-feeder digestion. Envi-ronmental Science and Technology 30, 2641–2645.
Mayer, L.M., Weston, D.P. & Bock, M.J. 2001. Benzo a pyrene and zinc solubilization by digestive fluids ofbenthic invertebrates — a cross-phyletic study. Environmental Toxicology and Chemistry 20,1890–1900.
McDonald, P., Cook, G.T. & Baxter, M.S. 1992. Natural and anthropogenic radioactivity in coastal regionsof the UK. In The Natural Radiation Environment. Fifth International Symposium on the NaturalRadiation Environment, Salzburg (Austria), 22-28. Sep. 1991, A. Janssens et al. (eds). Ashford, U.K.:Nuclear Technology Publishing, 707–710.
McKnight, D.G. 1969. A recent, possibly catastrophic burial in a marine molluscan community. New ZealandJournal of Marine and Freshwater Research 3, 177–179.
McManus, J. 1998. Temporal and spatial variations in estuarine sedimentation. Estuaries 21, 622–634.Meador, J.P., Stein, J.E., Reichert, W.L. & Varanasi, U. 1995. Bioaccumulation of polycyclic aromatic hydro-
carbons by marine organisms. Reviews of Environmental Contamination and Toxicology 143, 79–165.Moore, K.A., Wetzel, R.L. & Orth, R.J. 1997. Seasonal pulses of turbidity and their relations to eelgrass
(Zostera marina L) survival in an estuary. Journal of Experimental Marine Biology and Ecology 215,115–134.
Moore, P.G. 1977. Inorganic particulate suspensions in the sea and their effects on marine animals. Ocean-ography and Marine Biology: An Annual Review 15, 225–363.
Mudge, S.M. 2002. Reassessment of the hydrocarbons in Prince William Sound and the Gulf of Alaska:identifying the source using partial least-squares. Environmental Science and Technology 36, 2354–2360.
Naidoo, G. & Chirkoot, D. 2004. The effects of coal dust on photosynthetic performance of the mangrove,Avicennia marina in Richards Bay, South Africa. Environmental Pollution 127, 359–366.
Neff, J.M. 1979. Polycyclic Aromatic Hydrocarbons in the Aquatic Environment. Essex, U.K: Applied SciencePublishers Ltd.
Newcombe, C.P. & Jensen, J.O.T. 1996. Channel suspended sediment and fisheries: a synthesis for quantitativeassessment of risk and impact. North American Journal of Fisheries Management 16, 639–727.
Newcombe, C.P. & MacDonald, D.D. 1991. Effects of suspended sediments on aquatic ecosystems. NorthAmerican Journal of Fisheries Management 11, 72–82.
Nichols, C.R. 1974. Development document for proposed effluent limitations guidelines and new sourceperformance standards for the steam electric power generating point source category. Duluth, U.S.:United States Environmental Protection Agency Report No. EPA 440/1-73-029.
Norkko, A., Hewitt, J.E., Thrush, S.F. & Funnell, G.A. 2001. Benthic-pelagic coupling and suspension-feedingbivalves: linking site-specific sediment flux and biodeposition to benthic community structure.Limnology and Oceanography 46, 2067–2072.
Norton, M.G. 1985. Colliery-waste and fly-ash dumping off the northeastern coast of England. In Wastes inthe Ocean. Volume 4. Energy Wastes in the Ocean, I.W. Duedall et al. (eds). New York: John Wileyand Sons, 423–448.
O’Connor, T.P. 2002. National distribution of chemical concentrations in mussels and oysters in the USA.Marine Environmental Research 53, 117–143.
MICHAEL J. AHRENS & DONALD J. MORRISEY
120
Paine, M.D., Chapman, P.M., Allard, P.J., Murdoch, M.H. & Minifie, D. 1996. Limited bioavailability ofsediment PAH near an aluminum smelter: contamination does not equal effects. EnvironmentalToxicology and Chemistry 15, 2003–2018.
Pautzke, C.F. 1937. Studies on the effect of coal washings on steelhead and cutthroat trout. Transactions ofthe American Fisheries Society 67, 232–233.
Pearce, B.C. & McBride, J. 1977. A preliminary study on the occurrence of coal dust in Roberts Bank sedimentsand the effect of coal dust on selected fauna. FMS Technical Report Series. PAC/T-77-17. (Cited inHillaby 1981, no further citation information given.)
Pearson, T. H. & Rosenberg, R. 1978. Macrobenthic succession in relation to organic enrichment and pollutionof the marine environment. Oceanography and Marine Biology: An Annual Review 16, 229–311.
Perkins, E.J. 1976. The evaluation of biological response by toxicity and water quality assessments. In MarinePollution, R. Johnston (ed.). London: Academic Press, 505–585.
Persaud, D., Jaagumagi, R. & Hayton, A. 1993. Guidelines for the protection and management of aquaticsediment quality in Ontario. Toronto, Ontario, Canada: Ontario Ministry of the Environment, WaterResources Branch.
Peterson, C.H. 1985. Patterns of lagoonal bivalve mortality after heavy sedimentation and their paleoecologicalsignificance. Paleobiology 11, 139–153.
Ports Corporation of Queensland 2002. Port of Hay Point Environmental Management Plan. Brisbane: PortsCorporation of Queensland. Online. Available HTTP: http://www.pcq.com.au/2004/ports_haypoint.cfm(accessed 30 June 2004).
Preen, A.R., Lee Long, W.J. & Coles, R.G. 1995. Flood and cyclone related loss, and partial recovery, ofmore than 1000 km2 of seagrass in Hervey Bay, Queensland, Australia. Aquatic Botany 52, 3–17.
Querol, X., Juan, R., Lopez-Soler, A., Fernandez-Turiel, J. & Ruiz, C.R. 1996. Mobility of trace elementsfrom coal and combustion wastes. Fuel 75, 821–838.
Rao, P.D. & Walsh, D.E. 1997. Nature and distribution of phosphorus minerals in Cook Inlet coals, Alaska.International Journal of Coal Geology 33, 19–42.
Rao, P.D. & Walsh, D.E. 1999. Influence of environments of coal deposition on phosphorus accumulation ina high latitude, northern Alaska, coal seam. International Journal of Coal Geology 38, 261–284.
Reid, D.F. & Meadows, G.A. 1999. Proceedings of the Workshop: The Environmental Implications of CargoSweeping in the Great Lakes. NOAA Technical Memorandum ERL GLERL 114, 1–4.
Rendig, V.V. & Taylor, H.M. 1989. Principles of Soil-Plant Interrelationships. New York: McGraw-Hill.Salomons, W. & Förstner, U. 1984. Metals in the Hydrocycle. Berlin: Springer-Verlag.Santschi, P.H., Nixon, S., Pilson, M. & Hunt, C. 1984. Accumulation of sediments, trace metals (Pb, Cu) and
total hydrocarbons in Narragansett Bay, Rhode Island. Estuarine Coastal and Shelf Science 19, 427–449.Scavia, D., Field, J.C., Boesch, D.F., Buddemeier, R.W., Burkett, V., Cayan, D.R., Fogarty, M., Harwell, M.A.,
Howarth, R.W., Mason, C., Reed, D.J., Royer, T.C., Sallenger, A.H. & Titus, J.G. 2002. Climatechange impacts on U.S. coastal and marine ecosystems. Estuaries 25, 149–164.
Schulz, H.M. 1997. Coal mine workers’ pneumoconiosis (CWP): in vitro study of the release of organiccompounds from coal mine dust in the presence of physiological fluids. Environmental Research 74,74–83.
Scullion, J. & Edwards, R.W. 1980. The effects of coal industry pollutants on the macroinvertebrate fauna ofa small river in the South Wales coalfield. Freshwater Biology 10, 141–162.
Shaw, D.G. & Wiggs, J.N. 1980. Hydrocarbons in the intertidal environment of Kachemak Bay, Alaska. MarinePollution Bulletin 11, 297–300.
Shelton, R.G.J. 1973. Some effects of dumped solid wastes on marine life and fisheries. In North Sea Science,NATO North Sea Conference, Aviemore, Scotland (15–20 November 1971), D.D. Goldberg (ed.).Cambridge, U.S.: MIT Press, 415–436.
Short, J.W., Kvenvolden, K.A., Carlson, P.R., Hostettler, F.D., Rosenbauer, R.J. & Wright, B.A. 1999. Naturalhydrocarbon background in benthic sediments of Prince William Sound, Alaska: oil vs. coal. Envi-ronmental Science and Technology 33, 34–42.
Siboni, N., Fine, M., Bresler, V. & Loya, Y. 2004. Coastal coal pollution increases Cd concentrations in thepredatory gastropod Hexaplex trunculus and is detrimental to its health. Marine Pollution Bulletin 49,111–118.
UNBURNT COAL IN THE MARINE ENVIRONMENT
121
Sim, P.G. 1977. Concentrations of some trace elements in New Zealand coals. New Zealand Department ofScientific and Industrial Research (DSIR) Bulletin 218, 132–137.
Smith, F. & Witman, J.D. 1999. Species diversity in subtidal landscapes: maintenance by physical processesand larval recruitment. Ecology 80, 51–69.
Solid Energy New Zealand Ltd. 2002. Specifications of typical New Zealand semi-soft, Stockton coking coaland Stockton high energy thermal coal. Christchurch, New Zealand: Solid Energy New Zealand.Online. Available HTTP: http://www.coalnz.com/coal-specs.htm (accessed 1 November 2002).
Soong, R. & Berrow, M.L. 1979. Mineral matter in some New Zealand coals 2. Major and trace elements insome New Zealand coal ashes. New Zealand Journal of Science 22, 229–233.
Srivastava, S.K., Mahto, A.K. & Mahto, P. 1994. Physico-chemical characteristics of the river Damodar nearGiridih and Dhanbad districts of Bihar. Environment and Ecology 12, 839–842.
Stahl, R.G.J. & Davis, E.M. 1984. The quality of runoff from model coal piles. Journal of Testing andEvaluation 12, 163–170.
Stahl, R.G.J., Liehr, J.G. & Davis, E.M. 1984. Characterization of organic compounds in simulated rainfallrunoffs from model coal piles. Archives of Environmental Contamination and Toxicology 13, 179–190.
Stoker, P.W., Larsen, J.R., Booth, G.M. & Lee, M.L. 1985. Pathology of gill and liver tissues from two generaof fishes exposed to two coal-derived materials. Journal of Fish Biology 27, 31–46.
Swaine, D.J. 1977. Trace elements in coal. In Symposium on Trace Substances in Environmental Health-XI,D.D. Hemphill (ed.). Columbia, U.S.: University of Missouri, 107–116.
Swaine, D.J. 1990. Trace Elements in Coal. London: Butterworths.Swaine, D.J. & Goodarzi, F. (eds). 1995. Environmental Aspects of Trace Elements in Coal. Dordrecht: Kluwer.Swartz, R.C., Ferraro, S.P., Lamberson, J.O., Cole, F.A., Ozretich, R.J., Boese, B.L., Schults, D.W., Behrenfeld,
M. & Ankley, G.T. 1997. Photoactivation and toxicity of mixtures of polycyclic aromatic hydrocarboncompounds in marine sediment. Environmental Toxicology and Chemistry 16, 2151–2157.
Swift, M.C. 1985. Effects of coal pile runoff on stream quality and macroinvertebrate communities. WaterResources Bulletin 21, 449–457.
Sydor, M. & Stortz, K. 1980. Sources and transports of coal in the Duluth-Superior harbor. Duluth, U.S.:Environmental Research Laboratory, Office of Research and Development, United States Environ-mental Protection Agency, Report No. EPA-600/3-80-007.
Tadmor, J. 1986. Radioactivity from coal-fired power plants: a review. Journal of Environmental Radioactivity4, 177–204.
Talley, J.W., Ghosh, U., Tucker, S.G., Furey, J.S. & Luthy, R.G. 2002. Particle-scale understanding of thebioavailability of PAHs in sediment. Environmental Science and Technology 36, 477–483.
Tan, B. & Coler, R.A. 1986. Effects of coal pile leachate on Taylor Brook in western Massachusetts.Environmental Toxicology and Chemistry 5, 897–903.
Tease, B. & Coler, R.A. 1984. The effect of mineral acids and aluminum from coal leachate on substrateperiphyton composition and productivity. Journal of Freshwater Ecology 2, 459–467.
Terrados, J., Duarte, C.M., Fortes, M.D., Borum, J., Agawin, N.S.R., Bach, S., Thamanya, U., Kamp-Nielsen,L., Kenworthy, W.J., Geertz-Hansen, O. & Vermaat, J. 1998. Changes in community structure andbiomass of seagrass communities along gradients of siltation in SE Asia. Estuarine Coastal and ShelfScience 46, 757–768.
Tien, J.C. & Kim, J.Y. 1997. Respirable coal dust control using surfactants. Applied Occupational Environ-mental Hygiene 12, 957–963.
Tiwary, R.K. 2001. Environmental impact of coal mining on water regime and its management. Water Airand Soil Pollution 132, 185–199.
Tripp, B.W., Farrington, J.W. & Teal, J.M. 1981. Unburned coal as a source of hydrocarbons in surfacesediments. Marine Pollution Bulletin 12, 122–126.
U.S. EPA/U.S. ACE 1991. Evaluation of dredged material proposed for ocean disposal. Washington, D.C.:United States Environmental Protection Agency/United States Army Corp of Engineers, Report No.EPA 503/8-91/001.
U.S. EPA/U.S. ACE 1998. Evaluation of dredged material proposed for discharge in waters of the U.S. —Testing manual. Washington, D.C.: United States Environment Protection Agency/U.S. Army Corpsof Engineers Report No. EPA 823-B-98-004.
MICHAEL J. AHRENS & DONALD J. MORRISEY
122
Uthe, J.F. & Musial, C.J. 1986. Polycyclic aromatic hydrocarbon contamination of American lobster, Homarusamericanus, in the proximity of a coal-coking plant. Bulletin of Environmental Contamination andToxicology 37, 730–738.
Van Kooten, G.K., Short, J.W. & Kolak, J.J. 2002. Low-maturity Kulthieth Formation coal: a possible sourceof polycyclic aromatic hydrocarbons in benthic sediment of the northern Gulf of Alaska. EnvironmentalForensics 3, 3–4.
Verhaar, H., van Leeuwen, C.J. & Hermens, J. 1992. Classifying environmental pollutants. 1. Structure-activityrelationships for prediction of aquatic toxicity. Chemosphere 25, 471–491.
Vermaat, J., Agawin, N.S.R., Fortes, M.D., Uri, J.S., Duarte, C.M., Marbà, N., Enriquez, S. & van Vierssen,W. 1996. The capacity of seagrasses to survive increased turbidity and siltation: the significance ofgrowth form and light use. Ambio 25, 499–504.
Voparil, I.M. & Mayer, L.M. 2000. Dissolution of sedimentary polycyclic aromatic hydrocarbons into thelugworm’s (Arenicola marina) digestive fluids. Environmental Science and Technology 34, 1221–1228.
Wachter, R.A. & Blackwood, T.R. 1978. Source assessment: water pollutants from coal storage areas. Cin-cinnati, U.S.: Industrial Environmental Research Laboratory, United States Environmental ProtectionAgency, Report No. EPA 600/2-78-004M.
Wang, W.X. 2002. Interaction of trace metals and different marine food chains. Marine Ecology ProgressSeries 243, 295–309.
Wang, W.X. & Fisher, N.S. 1999. Delineating metal accumulation pathways for marine invertebrates. Scienceof the Total Environment 237, 459–472.
Ward, C.R. 1984. Coal Geology and Coal Technology. Melbourne: Blackwell Scientific.Ward, C.R. 2002. Analysis and significance of mineral matter in coal seams. International Journal of Coal
Geology 50, 135–168.Wilber, D. & Clarke, D. 2001. Biological effects of suspended sediments: a review of suspended sediment
impacts on fish and shellfish with relation to dredging activities in estuaries. North American Journalof Fisheries Management 21, 855–875.
Williams, R. & Harcup, M.F. 1974. The fish populations of an industrial river in South Wales. Journal of FishBiology 6, 395–414.
Williamson, R.B. & Morrisey, D.J. 2000. Stormwater contamination of urban estuaries. 1. Predicting the build-up of heavy metals in sediments. Estuaries 23, 56–66.
Wolanski, E. 1995. Transport of sediment in mangrove swamps. Hydrobiologia 295, 31–42.Wood, C.M. 2001. Toxic Responses of the Gill. Washington, D.C.: Taylor & Francis.World Coal Institute. 2004. Coal — Power for Progress. London: World Coal Institute. Online. Available
HTTP: http://www.wci-coal.com (accessed 30 June 2004).Young, B.M. & Harvey, L.E. 1996. A spatial analysis of the relationship between mangrove (Avicennia marina
var. australasica) physiognomy and sediment accretion in the Hauraki Plains, New Zealand. EstuarineCoastal and Shelf Science 42, 231–246.
Zhang, G., Du, W. & Wen, W. 1995. An estimation of the effects from coal dust of the coal wharf at a certainpower plant on the marine environment. Tropic Oceanology 14, 90–95.