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Chemical hazard identification and assessment tool for
evaluation of stormwater priority pollutants
E. Eriksson, A. Baun, P.S. Mikkelsen and A. Ledin
Environment & Resources DTU, Technical University of Denmark, Bygningstorvet, Build. 115,
DK-2800 kgs. Lyngby, Denmark (E-mail: eve@er.dtu.dk;anb@er.dtu.dk;psm@er.dtu.dk;anl@er.dtu.dk)
Abstract Assessment of chemical hazards is a critical issue, which have to be dealt with when
evaluating different strategies for sustainable handling of stormwater. In the present study, a
methodology for identifying the most critical and representative chemical pollutants was developed.
A list of selected stormwater priority pollutants (SSPP-list) is the out-put from the procedure. Two
different strategies for handling of stormwater were considered; discharge into a surface water
recipient and infiltration. However, the same methodology can be used for other types of wastewater
and other strategies for handling and treatment. A literature survey revealed that at least 656
xenobiotic organic compounds (XOCs) could be present in stormwater. In the next step, 233 XOCs
were evaluated with respect to the potential for being hazardous towards either aquatic living
organisms or humans, or causing technical or aesthetical problems. 121 XOCs were found have at
least one of these negative effects, while 26 XOCs could not be assessed due to the lack of data.
The hazard assessment showed that 40 XOCs had a PEC/PNEC ratio above one., e.g. they should
be considered as priority pollutants. The final step is the expert judgement, which resulted in a final
SSPP-list containing 16 selected priority pollutants.
Keywords Stormwater handling; hazard identification and assessment; xenobiotic organic compounds
Introduction
There is a growing demand in society for introducing decentralised systems providing
opportunities to save and reuse water. This development is driven by water shortage in
several parts of the world, but also by awareness that the centralised urban water systems
used for treatment of both stormwater and wastewater are expensive and resource
consuming. One way to reduce the need for freshwater and at the same time reduce the urban
runoff peak flows is to collect and use stormwater. Outdoors, a number of both structural and
non-structural BMPs (best management practises) may be used for handling of stormwater,
e.g. gullypots, retention/detention ponds, infiltration systems (porous paving and porous
asphalt surfaces, swales, infiltration trenches), basins, ponds and wetlands. Most of these
BMPs are constructed to reduce the risk for stormwater flooding. However, major limitations
with regard to both the use of collected stormwater and treatment in BMPs are the chemical
risks related to the handling of water with poor quality. The content of different types of
pollutants (chemical, physical and microbiological) is largely determined by the type of
surfaces the stormwater get in contact with (roofs, roads, parking lots, pavements etc.), but
also by the air quality, as well as human and animal activities at a specific site. Each pollutant
may lead to potential problems depending on the usage in question, either hazards regarding
exposure to humans, animals, crops or plants, or technical and aesthetical problems.
The present study aims to develop a screening procedure for identification and assessment
of the most critical pollutants regarding different strategies for handling of different types of
storm- and wastewater, i.e. a chemical hazard and problem identification and assessment
procedure aimed at identifying priority pollutants. The work presented in this paper is, due to 47
Water Science and Technology Vol 51 No 2 pp 47–55 ªIWA Publishing 2005
space limitations, restricted to one category of pollutants; the xenobiotic organic compounds
(XOCs) and to two strategies for handling of stormwater; discharge of untreated stormwater
to a surface water recipient and infiltration.
Methodology
Risk assessment of chemicals is composed of four elements: hazard/problem identification,
hazard/problem assessment, risk characterisation and risk management according to the
technical guidance document for risk assessment of chemicals in EU (TGD; European
Commission, 2003). In general, hazard identification serves to map the inherent properties of
chemicals by collecting and comparing relevant data on e.g. physical state, volatility and
mobility as well as potential for degradation, bioaccumulation and toxicity. Hazard
assessment is divided between exposure assessment and effect assessment. Comprehensive
model systems have been developed to assess the distribution of contaminants in the
environment (soil, water, air) and in tissue (animals, humans). The next step is risk char-
acterisation, where the potential negative effects are evaluated and, if possible, the prob-
ability of effects occurring is estimated. Finally, risk management involves a range of
possible interventions, i.e. monitoring and control of emissions to reduce risk environments
(see e.g. Mikkelsen et al., 2001).
The methodology developed in the present work is inspired by the TGD (European
Commission, 2003) and consists of five steps; (1) source characterisation, (2) receptor and
exposure identification, (3) hazard and problem identification, (4) hazard assessment and (5)
expert judgement, see Figure 1.
Source characterisation
Initially, information regarding potential pollutants (metals, inorganic trace elements and
XOCs) is collected. This is performed by two somewhat different approaches in the present
study.
(1) Searching in the open international literature regarding observations/measurements of
XOCs in stormwater collected from roofs, parking lots, roads and pavements. This is
generating a list of observed constituents (for more details see Eriksson et al., in
preparation).
(2) Searching in the literature regarding XOCs that potentially could be present in storm-
water due to e.g. contact with surfaces or human activities (car driving, gardening, etc.)
i.e. potentially present constituents. Four major sources for pollutants in stormwater
were considered; atmospheric deposition, releases from materials, human activities and
excretion from animals (Figure 2). The international literature and material databases
(e.g. BPS-Centret, 1998) were searched for information regarding the presence of XOCs
that potentially could be released from these sources (for more details see Ledin et al.,
2004).
Figure 1 Approach for selecting priority pollutants based on chemical hazard identification and
assessment
48
E. Eriksson et al.
All observed and potentially present constituents are listed as potential pollutants and
evaluated in the third step: hazard identification (Figure 1).
Receptor and exposure identification
In this step the different strategies for handling of the selected type of waste- and/or
stormwater will be evaluated with respect to potential human health hazards, technical and
aesthetical problems as well as environmental hazards that could occur due to the presence of
the chemical pollutants. Use, treatment or discharge scenarios will be investigated in order to
identify the potential exposure routes and what or who are exposed. Legislation is reviewed,
for each scenario, to elucidate the quality and emission standards.
Examples of receptors of relevance are humans as well as aquatic and terrestrial living
organisms. Exposure route for humans’ are oral intake, inhalation of aerosols and skin
contact. Continuous or pulse emissions need to be taken into account when evaluating BMPs
and discharges to the environment. In technical installations problems like precipitation,
corrosion and clogging are identified, i.e. technical installations have to be considered as
receptors as well.
Hazard and problem identification
All constituents identified as potential pollutants in the first step of the procedure (Figure 1)
are evaluated in the third step; the hazard and problem identification. The criteria for
evaluation are based on environmental fate (sorption, volatilisation, persistence to degra-
dation, bioaccumulation and toxicity) and long-term chronic effects to living organisms
(carcinogenicity, mutagenicity, reproduction hazards and endocrine disrupting effects) as
well as promoting allergic reactions in humans. Precipitation of salts and corrosion of
different types of installations and tubing are examples of relevant technical problems that
Atmospheric
deposition
Release from
materials
Human/animal
activities
Dry Wet Buildings VehiclesRoads Excre-
ments
Chemical
dispersion
Construction,
roofing felts/
tiles, bricks,
metal roofs,
drainpipes, roof
cements,
thatched roofs ,
concrete,
cements, wood,
plastics, wood
impreg. Agents,
paint/varnish,
pigments, filling
materials,
welds/joints,
putty, glues,
rock/mineral
wool, window
profiles/glass,
doors, facings,
tanks/reservoirs
Asphalt,
bitumen,
cement,
dust
Brakes, tires,
exhaust
fumes,
windscreen
washer
fluids, petrol,
oils,
crankcase
oils,
antifreeze
mixtures,
brake fluids
Pesticides,
road salts,
spillage,
fire-
extinguishing
agents,
gardening
fertilisers,
pest control
-
gutters and
-
Figure 2 Examples of sources that potentially are contributing to pollutants in stormwater
49
E. Eriksson et al.
should be included if inorganic constituents are considered in the study. Bad odour and
colouring of clothes and toilet bowls due to the presence of e.g. Fe- and Mn-precipitates or
humic and fulvic acids are examples of aesthetical problems to be considered.
The hazard and problem identification is performed according to a ranking methodology,
which is described in detail in Baun et al. (in preparation). The methodology consists of a
decision tree in which hazardous and problematic compounds are identified. To visualize the
sorting of XOCs the decision tree can be described as a funnel fitted with several filters. The
filters have been set according to specified criteria based on sorption, volatility, persistence
to biodegradation, potential for bioaccumulation and toxicity. There are also one on/off filter
for technical/aesthetical problems and a long-term chronic effects-filter considering cancer,
mutagenic and reproduction hazards, endocrine disruption effects and allergenic effects. The
output is a classification of the compounds in three categories (white, grey and black)
depending on their priority as possible pollutants. White compounds are considered as non-
priority pollutants, which means that these compounds will be excluded from the fourth step;
the hazard assessment. Grey compounds are passed on to the next filter. These compounds
may or may not be priority pollutants depending on the outcome of the following filtration.
Black compounds are considered as priority pollutants.
The first filter is designed to separate compounds into “water phase compounds” and
“solid phase compounds”. In this case the underlying assumption is that the water is trans-
ported in open systems facilitating good contact between air and water, i.e. highly volatile
compounds will be identified as white compounds, which is an acceptable assumption when
evaluating stormwater. It should be noted that no compound would be designated as black as
a result of this first filtration. The purpose with this filter is to “label” the XOCs according to
their preference for the water or the solid phase (e.g. suspended solids, sediment and soil).
This information will be used for the further evaluation in step 4; the hazard assessment.
Information required, in the present study, can mainly be collected from databases and
handbooks presenting the inherent properties of the XOCs, since only hazards towards
aquatic and soil living organisms are considered. The following references were used;
Hazardous Substances Database (2003); CCRIS (2003); Chemfinder (2003); Danish EPA
(2000); US EPA ECOTOX (2003); US EPA EPISUITE (2003); GENE-TOX database
(2003); IUCLID (2000); NOVA (2003); OSPAR (2003); Rippen (2003) and Verscheuren
(1996). The compounds that are identified as hazardous or problematic in this step are listed
as potential priority pollutants.
Hazard assessment
The exposure can be represented by predicted environmental concentrations (PEC), where
the values can be based on measured data or model simulations. Evaluation of the effects can
be relied on predicted no effect concentrations (PNEC). These represent estimated con-
centrations for which unacceptable effects are not likely to occur, and they can found in the
literature (databases and handbooks). Comparison between the PEC and PNEC values are
made in order to determine if the compound should be considered as hazardous for organisms
in the environment. The pollutants that receive a PEC/PNEC ration above one (1) are
classified as priority pollutants. A corresponding evaluation with respect to humans can be
performed by e.g. using acceptable daily in-take values, to retrieve effect-values. Possible
oversaturation of metal salts can be estimated by geochemical modelling (e.g. PHREEQC;
Parkhurst and Appelo, 2001). The pollutants that receive a saturation index above one
(oversaturated) are classified as priority pollutants. This step is not fully developed yet and
further refinement is part of on-going research.
As basis for a preliminary assessment measured concentrations found in the review by
Eriksson et al. (in preparation) were used in the present study to represent PEC-values.
50
E. Eriksson et al.
A dilution factor of 100 is used for the surface water discharge scenario according to the
suggestions in the TGD (European Commission, 2003). An assessment factor of 1000 (EU
Commission, 2003) is used when estimating PNEC values to the natural environment and to
compensate for transferring from laboratory tests and for inter-species variations of the test
organisms used. PNEC
soil
are calculated for each compound based on the Henry’s law
constant, the organic carbon-water partition coefficient (K
oc
) and the PNEC
water
.
Expert judgement
Finally, the expert judgement is performed. The “expert” is not necessarily a single person
(e.g. an environmental chemist) but may be a group of decision-makers with different
backgrounds. The idea is that the expert selects the priority pollutants for which further
action needs to be taken. The evaluation may e.g. aim at reducing the number of compounds
due to financial limitations in the specific project. Compounds may be removed based on use
patterns in the catchments or grouped based on similarity in structure and fate. In the latter
case, an indicator compound may be chosen to represent the whole group. Compounds that
are banned can also be removed unless certain reasons exist.
Legislation concerning limit values e.g. drinking water standards as well as environ-
mental quality standards and emission limit values for watercourses, lakes or the sea,
reviewed in step 2 (Figure 1) should be used in order to identify compounds that may need to
be added to the list. Compounds may also be added if they are priority pollutants present on
national/international lists or “special case” compounds. Compounds deriving from specific
anthropogenic sources e.g. car catalysts may also be added. Furthermore, high content of
easily degradable organic matter can cause odour, due to oxygen depletion and anaerobic
conditions, may require the presence of summary parameters as BOD and COD. Physical
parameters such as turbidity and temperature may also be needed in order to make complete
monitoring programme. The output from this step will be a list containing those chemical
compounds and other parameters that constitute a hazard after evaluation by the expert: the
selected priority pollutants.
Results and discussion
Source characterisation
The literature survey regarding observations and measurements of pollutants in stormwater
clearly showed that a large number of constituents have been identified and quantified. In
total, 173 publications were found in the open international literature (including e.g. the
review by Makepeace et al., 1995), which report all together 514 different constituents
(Eriksson et al., in preparation). In order to illustrate the diversity within the group of XOCs,
a division in subgroups, is given in Table 1. It should be mentioned that the searching carried
out within the project was limited (for more details see Ledin et al., 2004). Therefore, the
number of pollutants that potentially could be present would probably increase if the
searching was extended. There were a relatively limited number of compounds that belonged
to both groups, i.e. compounds that have been identified in stormwater and pointed out as
potentially present (Table 1). This observation indicates that although a large number of
organic compounds have been observed in stormwater, there could be at least as many other
compounds present, that no one has tried to analyse for yet.
Receptor and exposure identification
Two different scenarios for handling of stormwater were evaluated in the present study;
discharge to a surface water recipients and infiltration in the ground, i.e. the receptors for
consideration were surface water and soil. Accordingly, aquatic living organisms as well as 51
E. Eriksson et al.
soil organisms are going to be exposed to the pollutants. Groundwater quality was not
considered in this study.
Hazard and problem identification
It was found that at least 656 XOCs could potentially have an impact on the water quality
(Table 1). 233 XOCs (Baun et al., in preparation) have so far been evaluated according to the
hazard and problem identification procedure described above; 72 of these 233 XOCs were
classified as hazardous with regard to the water phase, whereas 88 were classified as
hazardous with respect to the solid phase (sediment, suspended solids or soil); 39 compounds
were overlapping between the two groups, which means that in total 121 XOCs are so far
identified as potentially hazardous. It should be noted that 26 XOCs could not be assessed
due to lack of data, either basic physical chemical data or environmental fate data. These
compounds require further data searching, testing or estimation by e.g. QSAR, in order to be
classified. The hazardous compounds in the solid phase mainly belonged to four different
groups: polycyclic aromatic hydrocarbons (PAHs), dioxins, chlorinated pesticides and
PCBs. The XOCs identified as hazardous in the water phase are more evenly distributed over
the 13 groups presented in Table 1. However, the major contribution is from the group with
pesticides.
Hazard assessment
In the hazard assessment, PEC-values for the 121 XOCs identified in the hazard and problem
identification step were compared with their corresponding PNEC-values. The XOCs are
considered as priority pollutants if the ratio exceeds 1. It was found that 99 of the potential
priority pollutants had been measured in stormwater according to the review by Eriksson
et al. (in preparation) and that the PEC/PNEC ratio exceeded one for 40 of them. The
majority were pesticides/herbicides, but a number of PAHs were also pointed out (e.g.
anthracene, benzo[a]pyrene, chrysene, naphthalene, pyrene and triphenylene), two phtha-
lates (DBP and DEHP), a polychlorinated biphenyl (PCB-153) as well as pentachlorophenol
(PCP).
More information regarding concentrations in stormwater, efficiency of treatment
methods, fate in receiving waters and soils, data for the effect analysis (human acceptable
daily doses and PNECs for ecosystems) is needed in order to refine this step.
Table 1 Number of compounds that have been identified in stormwater, number of potentially
present constituents, and the number that have been found in both categories
Compound group Compounds identified in
stormwater
“observed constituents”
Potentially present
pollutants
Number of constituents
present in both
categories
Alkanes 19 17 15
Benzenes 19 37 8
Dioxins 31 9 4
Ethers 8 7 1
Halogenated aliphates 27 25 8
Organotin compounds 0 9 0
Organolead compounds 9 0 0
PAHs 58 51 27
PCBs 14 0 0
Pesticides 115 64 26
Phenols 32 36 20
Phthalates and adipates 8 7 5
Miscellaneous 26 149 7
Total no. of constituents 366 411 121
52
E. Eriksson et al.
Expert judgement
Finally, the most important XOCs will be selected from the list with 40 XOCs identified in
the fourth step and other relevant XOCs can be added according to the judgement from the
experts involved. Among the herbicides/pesticides acrolein, dichlorprop, dichlorvos, diuron,
hexachlorocyclohexane (HCH), metazaklor, metoxyklor, propiconazol and terbutylazine
were selected (Table 2). The presence of these XOCs on EU Water Framework Directive list
“Priority substances in the field of water policy” (European Commission, 2004) was the
major reason for selecting these pesticides as they act as a representatives for groups of
pesticides, e.g. dichlorprop as a representative of fenoxy acids and correspondingly
metoxyklor for the chlorinated pesticides in use today. Naphthalene and benzo[a]pyrene
were selected among the PAHs. This grouping of PAHs was based on their ring structure in
order to ensure including a PAH present in both the aqueous phase and solid phase as well as
PAHs primarily found in the solid phase. Criteria such as high persistence, bioaccumulation,
and long-term chronic effects were also used in this evaluation. The other XOCs were
selected since they can act as indicator compounds of different pollutant groups (Table 2).
Long-term chronic effects, persistence and bioaccumulation as well as aesthetical problems
like odour were taken into consideration. Some of these are also on the list of priority
substances within EU’s Frame Water Directive (nonylphenol and DEHP). Among these were
NPEO, NP and MTBE added although they did not have PEC/PNEC rations above 1. It was,
however, judged that compounds with this property are needed in order to be able to evaluate
the impact from discharging or infiltrating stormwater.
This can be compared with the results from a corresponding work carried out for the
DayWater project (see the acknowledgement), where the major focus was to identify a list of
pollutants suitable for comparing different BMPs. Step 4 was excluded in this work, due to
the present limitations in this step (see above). The expert judgement was applied to the list
with 151 potential priority pollutants. After evaluation 3 PAHs, 4 herbicides, 1 PCB and 4
other XOCs as well as 13 physical/chemical parameters, metals and inorganic trace elements
were selected (Table 2). The evaluation was performed according to the following criteria.
Herbicides were selected from the list with potential priority pollutants based on use statistics
in Europe as well as observed presence in plants, animals and food products (Nordlander,
2003; Andersson et al., 2003; Danish EPA, 2003; Swedish Chemicals Inspectorate, 2003;
European Commission, 2004). Grouping of PAHs and selection of the other XOCs were
based on the same arguments as for the present study. The metals were selected to cover
both cationic and anionic species within the pH-range relevant for stormwater. Some
Table 2 List of selected stormwater priority pollutants: SSPP
Type of pollutants This study DayWater (excluding step 4)
General BOD, COD, suspended solids,
pH, nitrogen and phosphorus
Metals cadmium, chromium, copper,
nickel, lead, platinum and zinc
XOCs
Pesticides/
Herbicides
acrolein, dichlorprop, dichlorvos, diuron,
hexachlorocyclohexane (HCH), metazaklor,
metoxyklor, propiconazol and terbutylazine
glyphosate, pendimethalin,
phenmedipham and terbutylazine
PAH naphthalene, pyrene and
benzo [a] pyrene
naphthalene, pyrene and benzo
[a] pyrene
PCB PCB-153 PCB-28
Miscellaneous nonylphenolethoxylates and
nonylphenol, pentachlorophenol,
di (2-ethylhexyl) phthalate and
methyl tert-butyl ether,
nonylphenolethoxylates and
nonylphenol, pentachlorophenol,
di (2-ethylhexyl)
phthalate and methyl tert-butyl ether
53
E. Eriksson et al.
highly sorbing metals were included as well as non-sorbing ones. Specific sources (e.g. car
catalysts; and high observed loads in stormwater were also used as criteria for selection.
BOD, COD, suspended solids, pH and the nutrients are included since the general physical/
chemicals parameters are needed to e.g. evaluate technical/aesthetical problems.
Conclusions
The methodology developed within this study was found to be very promising. It can be used
generally for identifying selected priority pollutants (SSPP lists) for evaluation of different
strategies for handling of storm- and wastewater and for selection of priority pollutants to be
included in monitoring programmes. This procedure for selecting pollutants is transparent
and adaptive to the specific scenario in focus.
The study also showed that the number of XOCs that could be expected to be present in
stormwater is large (656 XOCs). However, it also illustrated that the XOCs that have been
identified and quantified in stormwater is probably only a fraction of those compounds that
are present; 366 have been observed by measurements and 411 have been identified as
potentially present, with an overlap of only 121 XOCs.
The hazard and problem identification carried out as a filtering further reduced the
number of relevant XOCs to 121, i.e. this is the potential priority pollutants. This part of the
study was hampered by the lack of inherent data for some of the potential pollutants. The
hazard assessment further reduced the number of relevant XOCs to 40. However, this step is
very preliminary, due to lack of data and procedures for exposure and effect assessment.
Finally, 16 XOCs were selected during the expert judgement. These have all inherent
properties that makes them potentially hazardous. Furthermore, some of them have been
observed in the environment in concentrations that could be critical for aquatic and soil
living organisms.
Acknowledgements
The results presented in this publication have been obtained within the framework of the EC
funded research project DayWater “Adaptive Decision Support System for Stormwater
Pollution Control”, contract no EVK1-CT-2002-00111, co-ordinated by Cereve at ENPC (F)
and including Tauw BV (Tauw) (NL), Department of Water Environment Transport at
Chalmers University of Technology (Chalmers) (SE), Environment & Resources DTU at
Technical University of Denmark (DTU) (DK), Urban Pollution Research Centre at
Middlesex University (MU) (UK), Department of Water Resources Hydraulic and Maritime
Works at National Technical University of Athens (NTUA) (GR), DHI Hydroinform, a.s.
(DHI HIF) (CZ), Ingenieurgesellschaft Prof. Dr. Sieker GmbH (IPS) (D), Water Pollution
Unit at Laboratoire Central des Ponts et Chausse
´es (LCPC) (F) and Division of Sanitary
Engineering at Lulea
˚University of Technology (LTU) (SE). The project is organised within
the “Energy, Environment and Sustainable Development” Programme in the 5th Framework
Programme for “Science Research and Technological Development” of the European
Commission and is part of CityNet, the cluster of European research projects on integrated
urban water management. Financial contribution from the Technical University of Denmark,
the Swedish MISTRA financed “Sustainable Urban Water Management” Programme and
the Danish Environmental Protection Agency is acknowledged.
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