2. About water@leeds
water@leeds is the water research centre at the University of Leeds.
Established in 2008, water@leeds provides research, training, education and
consultancy services across a range of water disciplines. Water Quality 2010 is
the first international conference organised by water@leeds.
The conference proceedings were prepared by water@leeds for the
participants of Water Quality 2010. Water Quality 2010 is supported by the
Worldwide Universities Network (WUN).
water@leeds will make this document available at this website (or by a link to
a different site). Any changes to its contents will be clearly recorded, either by
a note of corrigenda or the issue of a new edition, identified by an amended
report reference number and date.
Please cite as:
Water Quality 2010 (2010) Proceedings of the Water Quality 2010
Conference, 23-24 June, Weetwood Hall Hotel, Leeds, UK. water@leeds,
University of Leeds.
Available at: http://www.wateratleeds.org/water-quality-2010.php
Prepared by Water Quality Secretariat (R. Slack & S. Bowman)
Conference chairs: J. Holden, G. Czapar & Z. Zhang
water@leeds, 2010
water@leeds
School of Geography
University of Leeds
Leeds
LS2 9JT
UK
http://www.wateratleeds.org/water-quality-2010.php
Tel: +44 (0) 113 343 3373
Fax: +44 (0) 113 343 3308
Email: water@leeds.ac.uk
Online edition v.1
3. Contents
Page
Contents
Welcome 1
Programme 2
Biography of keynote speakers: 4
Presentations: 5
1. Management & Policy – Chair: Professor Joseph Holden 5
1.1 Integrated Water Demand Management: Innovative Approach Adopted by
Mercy Corps Organisation in Jordan – A. Assayed 5
1.2 An Assessment of Risks and Potential Measures for WFD Compliance in
Yorkshire’s Rivers – B. Crabtree 7
1.3 Water Policy in the UK: Impacts of Policy Development on Water Quality – J.
Marshall 11
1.4 Continental Scale Modelling of Water Quality in Rivers – R..Williams 13
2a. Treatment – Chair: Dr Miller Camargo-Valero 15
2.1 Improved Dye Adsorption for Water Treatment using the Arvia Process –
HMA Asghar 15
2.2 Using Intermittent Sand Filter for Grey Water Treatment: Case Studies in
Jordanian Rural Communities – A. Assayed 26
2.3 Application of Natural and Modified Materials for Treatment of Acid Mine
Drainage – AA. Bogush 28
2.4 Exploring the Potential of Agricultural Constructed Wetlands to Mitigate
Diffuse Pollution – C. Deasy 32
2b. Treatment – Chair: Dr Nigel Horan 36
2.5 Recovering Resources and Reducing the Carbon Footprint: a Better Way to
Deal with Wastewater Screenings – L.S. Cadavid 36
2.6 Natural Wastewater Treatment Systems for N Control and Recovery – M.
Camargo-Valero 38
3a. Monitoring, Ecosystems & Health – Chair: Dr Julian Dawson 39
3.1 Identification of Nitrate Sources in a Chalk Water Supply Catchment in
Yorkshire, UK – R. Grayson 39
3.2 Impacts of Artificial Drainage and Drain-blocking on Peatland Stream
Ecosystems – S. Ramchunder 40
3.3 Extraction and Analysis of Polycyclic Aromatic Hydrocarbons in the
Mediterranean Lebanese Seawater – A. Kouzayha 41
3b. Monitoring, Ecosystems & Health – Chair: Dr Paul Kay 50
3.4 Impacts of Agricultural Stewardship on Water Quality in Upland Catchments
P. Kay 50
3.5 Real Decisions on Water Quality: Monitoring and Modelling to an Appropriate
Level – F. Elwell 51
3.6 Evaluation of THMs Concentration and Cancer Risk Assessment in Tehran’s
Drinking Water – A. Pardakhti 52
4. Treatment: Part 2 – Chair: Dr David Adams 58
4. 4.1 The Use of Calligonium comosum Stems as a New Adsorbent Material for the
Removal of Toxic Cr(VI) Ions from Aqueous Media – M.A. Ackacha 58
4.2 Detection of Genes for Toxin Production in Cyanobacterial Strains Tested for
Sensitivity Towards Barley Straw Inhibition – J.Lalung 59
4.3 Biological Phosphorus Removal and Relevant Microorganism Charcteristics
of Sludge at Municipal Wastewater Treatment Plants, China – H. Wang 61
4.4 Nano-zeolite Formation from Coal Fly Ash and its Potential for Recovering
NH4+ and PO43- from Wastewater – X. Chen 62
5. Nutrients – Chair: Dr George Czapar 63
5.1 Long-term DOC Export from UK Peatlands – N.J.K. Howden 63
5.2 In-situ Measurement of Nutrient Dynamics and Cycling in Freshwaters - E.J.
Palmer-Felgate 65
5.3 Microcosmic Investigation on Characteristics and Mechanisms of Phosphorus
Cycling Between Water and Sediment Subjected to Warming – Z. Zhang 69
5.4 Are Climate Factors More Important than Nutrient Supply in Determining
River Phytoplankton Populations? – M.G. Hutchins 71
6. Tools – Chair: Dr Catherine Noakes 72
6.1 Catchment Monitoring Network Protects the Thames River – D. Hanson 72
6.2 Novel Combinations of Sensor Technology and Data Analysis for Safe
Drinking Water Production – M. Cauchi 73
6.3 What Can Complex Network Theory Tell Us About Water Quality in a
Distribution Network? D. Virden 75
7. Future Issues, New Initiatives – Chair: Dr James Marshall 78
7.1 Demonstration Test Catchments as a Means of Developing a Robust
Evidence Base for Catchment Management – B. Harris 78
7.2 How Effective is the Implementation of Controls on Diffuse Pollution Under
the Water Framework Directive in Scotland? Answers and Questions From
the Lunan Diffuse Pollution Monitored Catchment Project. – A. Vinten 80
7.3 Water Resource Planning and Climate Change Adaptation –A. Kemlo 84
8. Poster presentations 85
8.1 Bangladesh Water Problems and Probable Solutions – S. Akhter-Hamid 85
8.2 Variation and Transformation of Particulate Organic Carbon within the River
Dee Basin, NE Scotland – J.J.C. Dawson 87
8.3 Traditional vs. Molecular Methods for the Microbiological Analysis of Drinking
Water – A. Mohammad 89
8.4 Disinfection of E.coli Contaminated Waters Using Tungsten Trioxide-based
Photoelectrocatalysis – E.O. Scott-Emuakpor 91
8.5 Harvesting Rainwater Quality: a Case Study from Jordan – R.S. Shatnawi 94
8.6 Effects of Flow Conditions and System Geometry on Ammonium Removal
Rate and Ammonia Oxidisers Community Structure in Benthic Biofilms – K.
Yanuka 103
8.7 Determining the Trophic Structure and Water Quality by Phytoplankton
Composition and Environmental Factors of Sazlidere Dam (Istanbul, Turkey)
– a Drinking Water Source – N. Yilmaz 105
9. Workshop topics 106
10. Exhibitors at Water Quality 2010 107
YSI 107
RS Hydro 108
5. Delegate List 109
Conference Secretariat & Committee 111
6. Welcome note to WQ2010
On behalf of the Worldwide Universities Network (WUN) we are very pleased to
welcome you to Water Quality 2010. Your hosts this year are water@leeds at the
University of Leeds who will be delighted to help you if you have any queries during
or after the event. water@leeds is part of the WUN Water Quality Network and we
gratefully acknowledge WUN’s support in sponsoring this conference. We plan for
the conference to take place every two years at different venues as we move to
become the pre-eminent international water quality conference.
The conference has been organised to allow maximum time for networking and
discussion beyond the presentations, and we have included an afternoon of
workshops to help delegates to identify international collaborators to further develop
their research interests. The conference starts with three keynote speakers from the
United Kingdom, United States and China who will introduce the water quality issues
of concern in these countries. Following an initial plenary session concentrating on
water quality management, policy and research, the conference has adopted a
parallel session approach to provide delegates with a variety of different
presentations on a range of broad issues from water treatment, to understanding how
water quality impacts on the wider environment. Presentations on future issues and
novel tools lead into the workshop sessions.
Please use the collaboration form included in your delegate pack to feed information
back to the conference committee; this information will prove to be very useful during
the workshop sessions on 24 June. So, if you are looking for collaborators in a
particular area of water quality or have an idea that you would like to explore further
within this gathering of experts, please do use this form!
There are a number of opportunities for networking during the conference.
Refreshment breaks will take place in the area outside the conference rooms while
lunch will be served in the hotel restaurant. The poster presentation session on 23
June will be accompanied by a drinks reception and the conference dinner that
follows will take place in Weetwood Hall’s Jacobean Room. Weetwood has a number
of amenities that you are free to make use of, including garden, bar and courtyard
areas. Leeds city centre and the main university campus is short taxi ride away – the
conference secretariat can help with any enquiries you may have about local
attractions and facilities, from shopping to skiing!
With the goal of developing an international research community focused on
identifying, developing and delivering the best solutions to international water quality
problems, we hope you will also consider joining the WUN Water Quality Network.
Led by the Universities of Leeds, Illinois and Zhejiang, the Water Quality Network
seeks to develop cutting-edge research, training and education in water quality. Use
the collaboration forms to express your interest. We hope you enjoy the conference
and look forward to welcoming you back in 2012!
water@leeds – water research at the University of Leeds
1
7. Programme
DAY 1
10:00 Welcome (Prof Joseph Holden)
Room: Headingley Suite, Weetwood Hall Hotel, Leeds
10:05 Keynote 1 – Water quality in the UK (Prof Adrian McDonald)
10:25 Keynote 2 – Water quality in the US mid-West (Dr George Czapar)
10:45 Keynote 3 – Water quality in China (Dr Zhijian Zhang)
11:05 COFFEE
1. Management, policy and international modelling
Chair: Prof Joseph Holden
Room: Headingley Suite
11:25 Integrated water demand management: innovative approach adopted by Mercy
Corps Organisation in Jordan [Assayed, A]
11:50 An assessment of risks and potential measures for WFD compliance in Yorkshire's
rivers [Crabtree, B.]
12:15 Water policy in the UK - impacts of policy development on water quality
[Marshall, J.]
12:40 Continental scale modelling of water quality in rivers [Williams, R.]
13:05 Further Questions/Discussion
13:10 LUNCH
2a. Treatment 3a. Monitoring, ecosystem and health
Chair: Dr Miller Camargo-Valero Chair: Dr Julian Dawson
Room: Headingley 2 Room: Headingley 1
14:10 Improved dye adsorption for water Identification of nitrate sources in a chalk
treatment using the Arvia process water supply catchment in Yorkshire, UK
[Asghar, HMA] [Grayson, R.]
14:35 Using intermittent sand filter for Impacts of artificial drainage and drain-
greywater treatment: case studies in blocking on peatland stream ecosystems
Jordanian rural communities [Ramchunder, S.]
[Assayed, A]
15:00 Application of natural and modified Extraction and analysis of polycyclic
materials for treatment of acid mine aromatic hydrocarbons in the
drainage [Bogush, AA] Mediterranean Lebanese seawater
[Kouzayha, A.]
15:25 Exploring the potential of agricultural Further Questions/Discussion
constructed wetlands to mitigate
diffuse pollution [Deasy, C.]
15:50 Further Questions/Discussion
15:55 TEA
2b. Treatment 3b. Monitoring, ecosystem and health
Chair: Dr Nigel Horan Chair: Dr Paul Kay
Room: Headingley 2 Room: Headingley 1
16:15 General discussion Impacts of agricultural stewardship on
water quality in upland catchments
[Kay, P.]
16:40 Recovering resources and reducing Real decisions on water quality: monitoring
the carbon footprint: a better way to and modelling to an appropriate level
deal with wastewater screenings [Elwell, F]
[Cadavid, LS]
17:05 Natural wastewater treatment systems Evaluation of THMs concentration and
for N control and recovery cancer risk assessment in Tehran's drinking
[Camargo-Valero] water [Pardakhti, A.]
17:30 Further Questions/Discussion Further Questions/Discussion
17:45 POSTER PRESENTATIONS
Chair: Dr Rebecca Slack
Room: Headingley Suite
19:30 DINNER
2
8. DAY 2
09:15 Welcome to Day 2 Welcome to Day 2
4. Treatment: Part 2 5. Nutrients
Chair: Dr David Adams Chair: Dr George Czapar
Room: Headingley 2 Room: Headingley 1
09:20 The use of Calligonium comosum stems Long-term DOC export from UK
as a new adsorbent material for the peatlands [Howden, NJK]
removal of toxic Cr(VI) ions from
aqueous media [Ackacha, MA]
09:45 Detection of genes for toxin production In-situ measurement of nutrient dynamics
in cyanobacterial strains tested for and cycling in freshwaters
sensitivity towards barley straw inhibition [Palmer-Felgate, E.J.]
[Lalung, J.]
10:10 Biological phosphorus removal and Microcosmic investigation on
relevant microorganism charcteristics of characteristics and mechanisms of
sludge at municipal wastewater phosphorus cycling between water and
treatment plants, China [Wang, H.] sediment subjected to warming [Zhang,
Zhijian]
10:35 Nano-zeolite formation from coal fly ash Are climate factors more important than
and its potential for recovering NH4 and nutrient supply in determining river
PO4 from wastewater [Chen, Xiaoyan] phytoplankton populations?
[Hutchins, MG]
11:00 Further Questions/Discussion Further Questions/Discussion
11:05 COFFEE
6. Tools 7. New initiatives, future issues
Chair: Dr Catherine Noakes Chair: Dr Jim Marshall
Room: Headingley 2 Room: Headingley 1
11:30 Catchment Monitoring Network Protects Demonstration test catchments as a
the Thames River [Hanson, D.] means of developing a robust evidence
base for catchment management
[Harris, B.]
11:55 Novel combinations of sensor How effective is the implementation of
technology and data analysis for safe controls on diffuse pollution under the
drinking water production [Cauchi, M.] Water Framework Directive in Scotland?
Answers and questions from the Lunan
Diffuse Pollution Monitored Catchment
project. [Vinten, A]
12:20 What can complex network theory tell Water resource modelling and climate
us about water quality in a distribution change adaptation [Kemlo, A.]
network? [Virden, D.]
12:45 Further Questions/Discussion Further Questions/Discussion
12:50 LUNCH
13:50 Workshop
Global water quality: the big issues in a changing environment
Facilitators: Dr Rebecca Slack and Dr George Czapar
Room: Headingley Suite
15:30 TEA
16:00 FINAL WORD
Room: Headingley Suite
16:30 CLOSE
9. Keynote biographies
Water Quality 2010 is pleased to welcome three international keynote speakers to this
conference. All of the keynotes are experienced researchers working in fields with a
primary research interest in water quality and offer different perspectives on this global
issue.
Prof Adrian McDonald's research interests focus on environmental
management, with particular emphasis on the following fields:
resource assessment, natural hazards, microbial dynamics, water
colour processes and control, catchment planning and risk,
decision support systems, and water demand assessment.
Previous research experience also includes diffuse pollution
assessment and forecasting, biofuel futures in the energy
economy and alternative disputes resolution.
Professor Adrian McDonald
Professor of Environmental Management. University of Leeds
Dr George Czapar is the Water Quality Coordinator for University
of Illinois Extension. He served as the leader of the Strategic
Research Initiative (SRI) in Water Quality for the Illinois Council
on Food and Agricultural Research (C-FAR). This collaborative
research project focused on developing nutrient standards for
Illinois. Dr. Czapar also has an appointment as an Adjunct
Associate Professor in the Department of Crop Sciences, where
he teaches and advises students in the Off-Campus Graduate
Studies Program.
Dr George Czapar
Adjunct Associate Professor. University of Illinois Extension
Dr Zhijian Zhang has considerable research experience in water
quality issues, particularly the biogeochemistry of biogenic
elements in wetland ecosystems and nutrient removal from
wastewater by biological and/or chemical innovation. With over
40 publications, Dr Zhang had a particular interest in P, C and N-
cycling in wetland systems and the use of nano-materials to
improve water quality and aid nutrient removal.
Dr Zhijian Zhang
Associate Professor, College of Environmental and Resources Sciences
Zhejiang University
10. 1. Management & Policy
1.1 Integrated Water Demand Management: Innovative
Approach Adopted by the Mercy Corps Organisation
in Jordan
Shadi Bushnaq1, Rania Al-Zoubi1, Almoayied Assayed2 *
1
Mercy Corps Organization, Jordan P.O. Box 830684, Amman 11183 Jordan
2
University of Surrey, Guildford, Surrey GU2 7XH
* Corresponding author: Tel. 07879545917 (UK) Fax. 01483 686671
a.assayed@surrey.ac.uk
KEYWORDS: Water Demand Management, Community Based Organisation, Water
Harvesting Techniques, Revolving Loan Funds.
ABSTRACT
Water is a vital human need and a cornerstone for socioeconomic development. Yet,
millions of people around the world do not have access to clean and sufficient water.
Jordan is one of the poorest countries regarding water resources. The annual per
capita share of water for all uses is estimated at 160 m3 and is projected to decline to
only 91 m3 by the year 2025, putting Jordan in the category of having an absolute
water shortage.
In order to address the challenge of Jordan's limited water resources, the United
States Agency for International Development (USAID)-funded Mercy Corps will
implement the “Community Based Water Demand Management” Project. The project
has started in 2006 and will continue till 2011. This five-year project was designed to
enable communities in Jordan to improve water use efficiency through building the
local community-based organisations’ (CBOs) capacity to take the lead in promoting
and raising the awareness level of their constituents around Water Demand
Management (WDM).
Throughout the past three years of the project, 135 CBOs were each awarded grants
of $10,000. The selection process was done through a highly-competitive and
transparent approach and with the participation of relevant stakeholders. These
5
11. grants have been managed by the selected CBOs and operated as revolving loan
funds to support households and small farms to develop and implement water saving
and efficiency projects. The project started with building the leadership capacity of
the local CBOs in general project management and technical tools in formal training
settings. Management topics included proposal writing, project design and
implementation, feasibility studies and financial aspects of revolving loan funds.
Whereas, technical training covered the concept of water efficiency, water demand
management, water challenges in Jordan and a range of applied information on
rainwater harvesting (e.g. drinking water hygiene, maintenance, cost and size
calculations), drip irrigation, greywater treatment and residential network
maintenance. Additionally, CBOs have received on-the-job training through
continuous support, supervision and monitoring by project team members to ensure
smooth implementation.
Until June 2009, 2792 people received loans. Gender has been considered from the
early stages of project: among all the CBOs there were 25 CBOs having only women
members. Moreover, 20% of total loan recipients were women. The women
participated in many themes during the projects, i.e. decision making and capacity
building.
The types of projects funded were rainwater harvesting cisterns and reservoirs,
roman cistern rehabilitation, residential network maintenance, drip irrigation, small
agricultural canal maintenance, spring improvement, greywater treatment and other
small-scale, high impact water efficiency investments. During the first three years of
the project, the amount of rainwater harvested by on-site decentralised cisterns was
115,783 m3. However, in spite of the huge quantity of water saved through drip
irrigation and residential network maintenance, it was not calculated due to
interferences of many external factors which would cause bias calculations.
As a result, the project empowered CBOs to create and manage revolving loan funds
which have supported communities to adopt innovative water demand management
solutions. In addition, the project contributed to finding other water resources among
households which had significant impact on household economy and health.
Finally, the project adopted participatory approaches that allowed all stakeholders to
get involved in all stages. Technical and economic issues as well as social inclusion
were integrated in a sustainable manner that will pave the way towards a new
approach for water management at the local level which can be called “Integrated
Water Demand Management”.
6
12. 1.2 An Assessment of Risks and Potential Measures
for WFD Compliance in Yorkshire’s Rivers
Bob Crabtree*, Gerard Morris**, and Ed Bramely***
* WRc plc, Frankland Road, Swindon, SN5 8YF, UK
Bob.Crabtree@wrcplc.co.uk,
Tel. 01793 865035; Fax 01793 865001
** Gerard Morris, Environment Agency, Leeds, LS1 19PG
*** Ed Bramley, Yorkshire Water Services Ltd., Bradford, BD6 2LZ
KEYWORDS: Phosphate, SIMCAT, Water Framework Directive, Water Quality
Modelling, Yorkshire
ABSTRACT
Complying with the Water Framework Directive – the WFD – (EC, 2002) water quality
standards for ‘good ecological status’ potentially requires a range of Programmes of
Measures (PoMs) to control point and diffuse sources of pollution. The WFD will drive
improvements in water bodies over the next twenty years. It is vital to understand the
implications of the WFD for long term environmental planning, including the options
for improvements to stakeholder assets and the degree to which the requirements of
the WFD can be met.
Water quality modelling can be used to understand where the greatest impact in a
catchment can be achieved through ‘end of pipe’ and diffuse source reductions. This
information can be used to target cost-effective investment by water companies,
industry and those with responsibilities for agriculture and urban diffuse inputs. In the
UK, river water quality modelling with the Environment Agency’s SIMCAT model
(Environment Agency, 2008) is regarded as the best current approach to support
decision making for river water quality planning. SIMCAT is a numerical model that
describes the quality of river water throughout a catchment by using a combined
Monte-Carlo and deterministic process simulation approach to predict the behaviour
of the summary statistics of flow and water quality, such as the mean and a range of
percentiles, at any point in a catchment. SIMCAT is a one dimensional, steady state
model that can represent inputs from both point-source discharges and diffuse inputs
and can represent the in-river decay of pollutants.
7
13. Under the WFD, phosphate standards do not contribute to ‘good chemical status’ but
phosphate is one of the Annex VIII substances for ‘good ecological status’. A recent
WFD SIMCAT pilot catchment study (Crabtree et al, 2009) indicated that the WFD
water quality standards (UKTAG, 2006) for phosphate pose a major challenge to
achieving compliance by measures to control both point source and urban and non
urban diffuse pollution. Also, it is not certain that such measures could deliver cost-
effective ecological benefits as an outcome.
SIMCAT water quality models for the main river catchments of the Yorkshire Region
in the North East of England - the Hull, Aire, Don, Ouse, Derwent and Esk were
developed jointly by the Environment Agency and Yorkshire Water between 2003
and 2008. The models, produced by WRc, cover over 3000km of river reaches
designated under the WFD and are based on routine river and effluent monitoring
data for a 5 year period to give consistency within the suite of models. In addition, all
models are fully developed and calibrated to the same Environment Agency technical
specification. The models are being used to support both individual catchment and
regional scale water quality modelling studies for the WFD. In part, these studies are
considering the relative impacts of point source and diffuse pollution across each
catchment and, therefore, the potential benefits and costs of measures to reduce
both pollution sources, as necessary, to achieve WFD requirements.
A focus for an initial regional study was to identify the water quality benefits and
improved compliance with WFD standards for the 488 water bodies in the region that
could, potentially, be produced by point source sewage treatment works (STW)
discharge controls alone. A range of SIMCAT modelling scenarios were assessed:
1. all STWs operating at current actual performance;;
2. all STWs operating at current discharge consent limits for flow and quality;
3. all STWs operating at future planned discharge consent limits for flow and
quality; and,
4. all STWs operating at current Environment Agency technology limits for
phosphate removal (annual average 1 mg/l for population equivalent (PE) >
1000; annual average 2 mg/l for PE <1000; no limit applied to PE <250).
The results for scenario 1 indicate that, currently, 54% of Yorkshire’s rivers comply
with the WFD phosphate standards. Figure 1 shows the model predicted compliance
with WFD phosphate standards at Environment Agency monitoring sites.
8
14. Figure 1. SIMCAT predicted current phosphate compliance at WFD water quality
monitoring sites in Yorkshire.
The scenario 1 results also demonstrate that effluent discharges are the largest
source of phosphate in the more urbanised Aire, Don and Hull catchments but diffuse
pollution is the largest source in the more rural Ouse, Derwent and Esk catchments.
However, at a regional scale, diffuse pollution is the largest source of phosphate,
BOD, ammonia and nitrate. Figure 2 illustrates the regional source apportionment
assessment for phosphate.
Industrial
Discharges
2%
Current Actual
Total Load Input:
STW Discharges 9,889 kg/day
44%
Diffuse Sources
54%
Figure 2. Phosphate source input to Yorkshire Rivers.
Scenarios 2 and 3 give similar results to scenario 1 as only a small reduction in
phosphate would be produced. The results from scenario 4 indicate that phosphate
removal at current technology limits applied to all 256 STWs with PE>250 would
9
15. produce a reduction of 67% of the current total STW input and 32% of the current
total river load. This would result in an additional 298 km of rivers meeting the WFD
phosphate standards. However, this would only produce a 10% increase over current
predicted compliance.
The modelling results show that achieving compliance with WFD water quality
standards in the Yorkshire region will be a major technical and financial challenge.
Achieving full compliance, if appropriate, will require targeted investment in future
measures to reduce both point source and diffuse pollution across all catchments.
REFERENCES
Crabtree, R., Kelly, S., Green, H., Squibbs, G. and Mitchel. (2009). A case study
apportioning loads and assessing environmental benefits of programmes of
measures. Wat. Sci. Tech. 59.3, 407-416.
Environment Agency (2008). SIMCAT10.84 – A Guide and Reference for Users.
EC (2002). Council Directive of 23 October 2002 establishing a Framework for
Community Action in the Field of Water Policy (2000/60/EEC). Official Journal of the
European Communities, No.
UKTAG (2006). UK Environmental Standards and Conditions (Phase 1). Final Report
(SR1 – 2006), UK Technical Advisory Group on the Water Framework Directive
(www.wfduk.org).
ACKNOWLEDGEMENT
This paper has been produced with the permission of the Directors of WRc, the
Environment Agency, and Yorkshire Water Services. The views expressed in the
paper are those of the authors and not necessarily the views of these organisations.
10
16. 1.3 Water Policy in the UK – impacts of policy
development on water quality
James Marshall
Executive Business Adviser, Water UK, 1 Queen Anne’s Gate, London SW1H 9BT
Tel: 0207 344 1824, Mob: 07920 752344, E-mail: jmarshall@water.org.uk
KEYWORDS: water policy, UK, Europe, water companies
ABSTRACT
Drinking water quality in the UK is renowned for being one of the highest in Europe.
Each year over 99.95% of all samples taken in England and Wales comply with
national and European standards. To achieve this water companies have invested
heavily in water treatment and distribution technologies and upgrading networks.
2010 is an important year for water policy both in the UK and in Europe. Parliament is
currently (at the time of drafting the abstract) debating the Flood and Water
Management Bill which will address not just flooding issues but also legislation
around hosepipe bans and customer debt. Furthermore, towards the end of 2009
Defra received two strategic reports – the Cave report on competition and innovation
and the Walker report on charging and metering. If implemented in full these two
reports could instigate fundamental changes to the manner in which the UK water
industry is structured. In Europe the Drinking Water Directive is due for review and is
likely to formally introduce the concept of drinking water safety plans as well as
revise the parametric values of chemicals in drinking water. Coupled with this is a
new Biocide Regulation and associate procurement standards.
Water companies have recently commenced the 2010-2015 investment programme.
Infrastructure replacement rates are likely to be around 0.5% per annum, lower than
previous asset management plan (AMP) periods when significant water quality
undertakings drove investment. In England and Wales Ofwat have allowed for
around £1/3 billion investment in water treatment and a further £1/4 billion investment
in dealing with lead, colour, turbidity and iron.
This paper will consider whether 2010-15 will see the improvements in the quality of
our drinking water seen since 1990 continue or do we run a danger of becoming
bogged down in legislation, regulation and red tape?
11
17. BIBLIOGRAPHY
Future water and sewerage charges 2010-2015 Final Determinations, Ofwat. 2009.
Walker Review – Charging and metering for water services, Defra, 2009
(http://www.defra.gov.uk/environment/quality/water/industry/walkerreview/final-
report.htm)
Cave Review – Competition and innovation in water markets, Defra, 2009
(http://www.defra.gov.uk/environment/quality/water/industry/cavereview/documents/c
avereview-finalreport.pdf)
12
18. 1.4 Continental Scale Modelling of Water Quality
in Rivers
Richard Williams*1, Anja Voss**, Virginie Keller*, Ilona Bärlund**,
Olli Malve† and Frank Voss**
* Centre for Ecology and Hydrology, UK ** CESR, Universität Kassel, Germany †
Finnish Environment Institute (SYKE)
1
Centre for Ecology and Hydrology, Wallingford, Oxfordshire, OX10 9AU, UK.
Telephone: +44 (0)1491 692398, Fax: +44 (0)1491 692424, email: rjw@ceh.ac.uk
KEYWORDS: Water Quality, Global Scale, Gridded Model, BOD, Scenarios
ABSTRACT
Global and continental scale modelling has been confined to water quantity (e.g.
WaterGAP - Water Global Assessment and Prognosis (Alcamo et al. 2003), GWAVA
- Global Water AVailability Assessment (Meigh et al, 1999)). Here we describe an
approach to include water quality at these scales within the WaterGAP model. The
application is to the pan-European area and is being carried out within the EU-funded
SCENES Project which has the principal goal of developing new scenarios of the
future of freshwater resources in Europe.
The model operates on 5x5 arc-minute grid squares. Water flows in and between grid
cells are provided by WaterGAP. The water quality loadings into the river system
comprise point sources (domestic effluent, manufacturing discharges and urban
runoff) and diffuse sources (runoff from land and scattered settlements not connected
to the public sewerage system). Point source loadings are calculated for each
country using easily available datasets. For example, the domestic load is a per
capita emission factor times by country population multiplied by the percentage of the
population connected to the sewage system, which is then reduced by the amount
removed in each of three types of sewage treatment (primary, secondary and
tertiary). Data on the amount treated in different types of sewage works is set for
each country, while the amount removed by treatment types will vary with the water
quality variable being modelled. Country level data is converted to grid square data
required by the model, according to the population in each grid square. Diffuse
sources from land are calculated by regression models based on runoff and land use
(e.g. numbers of livestock) for each model grid square.
13
19. The modelling system has currently been set up to simulate biochemical oxygen
demand (BOD) and total dissolved solids. The model was tested against measured
longitudinal profiles and time series data for BOD on contrasting rivers e.g. the River
Thames (UK) driven by domestic loading and the River Ebro (Spain) with a high
share of discharges from livestock farming. Further developments will see the
inclusion of total nitrogen (TN), total phosphorus (TP) and dissolved oxygen.
Within the SCENES project a set of future scenarios reflecting different outlooks on
Europe has been developed, called “Economy First”, “Fortress Europe”,
“Sustainability Eventually” and “Policy Rules”. An Expert Panel was used to suggest
what these futures would mean for drivers of water quantity and water quality across
pan-Europe. We have projected how changes in percentage population connected to
sewers, the level of sewage treatment and population would change loadings from
domestic effluent for TN, TP and BOD. In time, these will be used to predict future
water quality in European rivers.
REFERENCES
Alcamo J., Döll P., Henrichs T., Kaspar F., Lehner B., Rösch T., and Siebert S.
(2003). Development and testing of the WaterGAP2 global model of water use and
availability. Hydrological Sciences Journal, 48: 317- 337.
Meigh J.R., McKenzie A.A. and Sene K.J., (1999). A grid-based approach to water
scarcity estimates for eastern and southern Africa. Water Resources Management,
13, 85-1 15.
14
20. 2a & 2b. Treatment
2.1 Improved Dye Adsorption for Water Treatment
Using the Arvia® Process
H. M. A. Asghar1*, S. N. Hussain1, E. P. L. Roberts1, A. K.
Campen2 and N. W. Brown2
1
Department of Chemical Engineering and Analytical Science, the University of
Manchester, P.O. Box 88, Manchester M60 1QD, UK
2
Arvia Technology Limited, Liverpool Science Park, Innovation Centre, 131 Mount
Pleasant, Liverpool, L3 5TF
*Corresponding Author:hafiz.asghar@postgrad.manchester.ac.uk
KEYWORDS: Water treatment, Arvia® process, Adsorption, Surface area,
Electrochemical regeneration.
ABSTRACT
The Arvia® process is a new technology for the treatment of water contaminated with
toxic or biologically non-degradable pollutants, using a carbon-based adsorbent
called Nyex®. Nyex® is a novel, non-porous and highly electrically conducting
adsorbent. This adsorbent material has been reported as being capable of simple,
quick and cheap electrochemical regeneration that makes it an economic adsorbent
for water treatment applications. The adsorptive characteristics of Nyex® materials
have been investigated at batch scale using an organic dye, Acid Violet 17, as the
adsorbate. The two Nyex® materials currently available have a relatively low specific
surface area (2.5 & 1 m2 g-1) and adsorptive capacities of 5 & 3.5 mg g-1 respectively.
These adsorptive capacities are significantly lower than that of activated carbon
materials which have specific surface areas of up to 2000 m2 g -1. The low surface
area of Nyex® is associated with its non-porous nature which also leads to the low
adsorptive capacity observed for Nyex® materials. This study is focussed on
improving the adsorption capacity of Nyex® materials through the development of
new adsorbents with high surface area and high electrical conductivity. The
adsorptive capacity and electrochemical regeneration characteristics have been
investigated using Acid Violet 17 as the adsorbate. Significant improvements in the
surface area (increased to 17 m2 g -1) and loading capacity of 9 mg g -1
have been
15
21. achieved for the adsorption of Acid Violet 17. These improved materials will enable a
reduction in the size and capital cost of the Arvia® process required to treat any given
effluent.
1. INTRODUCTION
Water contamination is becoming a worldwide problem due to rapid industrial growth.
Dyes are utilized by several industries such as textile, paper, printing, cosmetics,
pharmaceutical, rubber, food and plastics (Thinakaran et. al., 2007). The coloured
effluents of these industries may damage aquatic and human life as they inhibit
sunlight penetration into the water and reduce photosynthetic action. Some of the
dyes are carcinogenic and mutagenic (Sivaraj et. al., 2000). There are various
methods which are currently being used for colour removal e.g. biological,
coagulation, flocculation, chemical oxidation and adsorption. The removal of colour
from water by adsorption is considered the most efficient and economic way after
biological treatment. However, some of the dyes are resistent to biological
degradation due to their complex nature and synthetic origin.
In most cases activated carbon adsorption is used for colour removal. This process
has some limitations due to high cost and material loss during the thermal
regeneration process (Brown 2004). This has led researchers to work on low cost
materials for the development of adsorbents such as nut shell, fly ash, industrial and
agricultural waste etc. None of these adsorbents could be electrochemically
regenerated due to their low electrical conductivity (Kannan and Murugavel 2007,
Azhar et. al., 2005). Brown (2004) developed a new process for waste water
treatment with a unique combination of adsorption and electrochemical regeneration
in a single unit called the Arvia® process.
The Arvia® process is a newly developed technology for the treatment of water,
contaminated with toxic or biologically non-degradable pollutants, using graphite
based adsorbents called Nyex®. Brown successfully exploited this process for the
removal of phenol, crystal violet and atrazine from aqueous solutions (Brown 2004 a,
b and c). Brown also developed a range of graphite based adsorbents for water
treatment applications called Nyex® materials. These adsorbents were non-porous
and highly electrically conducting. However, they delivered a very small adsorption
-1
capacity, for example only 3.5 mg g for Acid Violet 17 in aqueous solution. The
focus of this study was to develop new adsorbents with improved adsorption capacity
and to evaluate the electrochemical regeneration capability of these materials for the
removal of Acid Violet 17 from aqueous solution.
16
22. 2. MATERIALS & METHODS
Nyex® 1000 is a low-cost graphite intercalation compound. Elemental analysis
®
indicates that Nyex 1000 is 98 % carbon content and particle size measurements
have determined the mean particle diameter to be 484 micrometre. It is non-porous,
and the BET surface area of Nyex® 1000 was determined by nitrogen adsorption and
found to be 1 m2 g1. Nyex® 500 is a newly developed graphite based adsorbent with
a mean particle size of 756 micrometre which is larger then Nyex® 1000 but aims to
have a higher adsorptive capacity. For reasons of commercial confidentiality, the
method of preparation of this material cannot be disclosed. It differs in its surface
morphology from Nyex® 1000. Nyex® 500 has some porosity, with a pore volume of
0.0684 cm3 g1. The BET surface area of Nyex® 500 was found to be significantly
higher than that of Nyex® 1000 at 17 m2 g-1.
The Acid Violet 17 dye used in this study was supplied by Kemtex Educational
Supplies under the trade name Kenanthrol Violet with a dye content of 22 %. The
Nyex® 1000 was supplied by Arvia® Technology Ltd. Adsorption and electrochemical
regeneration experiments were conducted in sequential batch reactor illustrated in
Figure 1. The comparative study of Nyex® 1000 and 500 comprised the following
steps.
Figure 1: Schematic diagram of sequential batch electrochemical cell
2.1 Adsorption kinetics
17
23. Batch adsorption experiments were carried out to determine the time required to
achieve equilibrium. A specified mass of Nyex® 1000 or 500 was added to samples
of aqueous solution of Acid Violet 17. The mixing was undertaken by sparging air
from the bottom of the cell. At regular intervals, 10 ml samples were taken, filtered
(Whatman GF/C filter paper) and analysed using a UV spectrophotometer.
2.2 Adsorption Isotherm Studies
Adsorption isotherms were determined by adding a fixed mass of Nyex® 1000 and
500 to 100 ml of various concentrations of acid violet solution ranging 10 to 200 mg l-
1
in a 250 ml flask. These flasks were stirred for 60 minutes at 700 rpm. After
adsorption, the solution was filtered and analysed using a UV spectrophotometer. In
order to compare the isotherms for both adsorbents, a Freundlich model fitted the
data using a least square error method.
2.3 Electrochemical regeneration
The electrochemical regeneration of the Nyex® 1000 and 500 adsorbents was
achieved in regeneration compartment of an electrochemical cell (Figure 1). The cell
was divided with a perforated 316 stainless-steel cathode separated from a graphite
anode (Arvia® Technology Ltd.) by a microporus Daramic 350 membrane. The anode
was placed 2 cm from the membrane with the active area of the anode being
dependent of the mass of adsorbent being regenerated, typically 5 cm 2. The
electrolyte in the cathode compartment was a 0.3 % w/w NaCl solution. The
regeneration procedure was as follows:
i) Initial adsorption: A known weight of Nyex® 1000 and 500 was added to 1000
ml of 500 and 800 mg l-1 Acid Violet solution into the batch cell for specified time
for equilibrium conditions. Air supply was provided for mixing. After adsorption,
the solid particles were allowed to settle down into the anodic compartment of the
sequential batch reactor. The equilibrium concentration of Acid Violet 17 after
adsorption and thus (by mass balance) the initial adsorbent loading qi was
determined.
ii) Electrochemical regeneration: Once the adsorbent material settled down into
the anode compartment of an electrochemical cell, a DC current of 1 Amp. was
supplied for 60 minutes for both the adsorbents. There was no flow in the cell and
the only mixing was due to the gas bubbles produced at the electrodes.
iii) Re-adsorption: Regenerated Nyex® 1000 and 500 (contents of anodic
compartment with no further treatment) were allowed to retain their adsorption
capacity by mixing with fresh Acid Violet 17 solution. After adsorption the
18
24. equilibrium concentration of Acid Violet 17 and thus (by mass balance) the
adsorbent loading after regeneration qr were determined. This loading was
always calculated assuming that the loading was zero prior to the adsorption test.
For multiple adsorption / electrochemical regeneration cycles, steps (ii) and (iii) were
repeated.
3. RESULTS & DISCUSSION
Adsorption kinetic studies using Acid Violet 17 / Nyex® 1000 and Acid Violet 17 /
Nyex® 500 were undertaken in order to estimate the equilibrium time required for
adsorption of Acid Violet 17 onto both Nyex® 1000 and 500 adsorbents. The
adsorption was found to be rapid (Figure 2) with more than (60 %) of the equilibrium
achieved within 5 minutes for both Nyex® 1000 and Nyex® 500 adsorbents. The rate
of adsorption was similar for both materials although the kinetics of adsorption on
Nyex® 1000 was slightly faster. In both cases it was found that 60 minutes contact
time was sufficient to achieve equilibrium.
Figure 2: Kinetic study for Acid Violet 17 using 20 g Nyex® 1000 and 10 g Nyex®
500 adsorbents, shaken in a 1000 ml flask with initial Acid Violet 17 concentrations of
75 and 70 mg l-1 respectively.
The adsorption isotherms (Figures 3 & 4) show the adsorptive capacity for both
adsorbents. Nyex® 500 delivered improved adsorption capacity of 8 to 9 mg g -1 to
that of Nyex® 1000 with adsorption capacity of 3.5 mg g-1. However, the particle
19
25. surface of Nyex® 500 is partially porous and that contributed to the enhancement of
surface area and improved loading capacity. Nyex® 500 was characterized with pore
volume 0.0684 cm3 g-1 and pore diameter of 163 A and while the pore volume of
Nyex® 1000 was very small at onoly 0.003778 cm3 g-1.The small surface area of
Nyex® 1000 and 500 [1 and 17 m2g-1] is responsible for low adsorption capacity when
compared with activated carbon whose surface area may range up to 2000 m 2g-1.
Although the adsorption capacity of the Nyex® materials is low, adsorption is rapid
and low cost regeneration can also be rapidly achieved. However, activated carbon is
not a suitable adsorbent for the Arvia® process as it is not capable of quick
electrochemical regeneration which is the key feature of Arvia® process. The
adsorption capacity of Nyex® 500 was increased by increasing surface area through
the formation of small pores on the surface of the particles. The newly developed
adsorbent material (Nyex® 500) is also highly electrically conducting, an essential
characteristic for its use in the Arvia® Process. High electrical conductivity of the
material ensures a low voltage drop through the adsorbent material during
electrochemical regeneration, and hence a low energy consumption.
Figure 3: Adsorption isotherm study for Acid Violet 17 onto Nyex® 1000 in a 250 ml
flask using a contact time of 60 minutes to achieve equilibrium
20
26. Figure 4: Adsorption isotherm study for Acid Violet 17 onto Nyex® 500 in a 250 ml
flask using a contact time of 60 minutes to achieve equilibrium
The Freundlich Eq. (1) was found to fit the isotherm data effectively. The Freundlich
constants (kf and 1/n) for both adsorbents were obtained from the log – log plot of the
solid phase equilibrium concentration (qe) versus liquid phase equilibrium
concentration (Ce), as shown in Figures 5 and 6. The kf and 1/n values for Nyex®
1000 and 500 were found to be 0.798, 2.3 and 1.74, 8.2 respectively.
qe k f C e
1 n
(1)
Figure 5: Freundlich model for the adsorption of Acid Violet 17 onto Nyex®1000
(concentration range of Acid Violet 17, 20 – 150 mgl-1)
21
27. Figure 6: Freundlich model for the adsorption of Acid Violet 17 onto Nyex®500
(concentration range of Acid Violet 17, 10 – 150 mg l-1)
The regeneration performance was characterised by determining the regeneration
efficiency:
qr
R.E (%) (100) (2)
qi
Where R.E stands for electrochemical regeneration efficiency in percent, while qr and
qi are the adsorbent loading determined after regeneration and the initial adsorbent
loading respectively, measured under a same set of conditions (initial concentration
of Acid Violet 17, solution volume and mass of adsorbent).
Nyex® 500 was found to be capable of electrochemical regeneration with the same
regeneration parameters maintained for Nyex® 1000, as shown in Figures 7 and 8.
For both materials regeneration efficiencies of ~100% were achieved over five cycles
of adsorption and regeneration. When no charge was passed during the
regeneration, the regeneration efficiency decreased as the adsorbent became
saturated with the Acid Violet 17 adsorbate. It has been concluded that the
electrochemical regeneration led to the anodic oxidation of adsorbed Acid Violet 17
on the surface of the Nyex® adsorbents. After the completion of electrochemical
regeneration, the contents are transferred to the next adsorption cycle without further
treatment. The products of electrochemical oxidation were predominantly carbon
dioxide and water released from the reaction zone during the electrochemical
regeneration process.
22
28. Figure 7: Regeneration efficiency (based on colour removal) over a number of
sequential adsorption and electrochemical regeneration cycles with Acid Violet 17 /
Nyex® 1000 using sequential batch cell. Operating parameters; Current 1 Amp.,
Treatment time 60 min. and Charge passed 36 C g-1
Figure 8: Regeneration efficiency (based on colour removal) over a number of
sequential adsorption and electrochemical regeneration cycles with Acid Violet 17 /
Nyex® 500 using sequential batch cell. Operating parameters; Current 1 Amp.,
Treatment time 60 min. and charge passed 80 C g-1.
4. CONCLUSIONS
This study has demonstrated the improved adsorption capacity of newly developed
Nyex® 500 for the removal of Acid Violet 17 when compared to the current material,
Nyex® 1000 used in the Arvia® process. An electrochemical regeneration efficiency of
~100% was achieved with a current of 1 A for 60 minutes, and a charge of 80 C g-1.
ACKNOWLEDGEMENT
23
29. This study was carried out with the support of Arvia® Technology Ltd. The authors
also wish to express their thanks to Dr. Sackakini of the Department of Chemistry,
the University of Manchester who carried out the surface area analysis and pore size
determination of Nyex® materials.
REFERENCES
Ahmad M. M. (2008), Electrochemical oxidation of acid yellow and acid violet dyes
assisted by transition metals modified kaolin. Portugaliae Electrochimica Acta 26/6
(2008) 547 – 557.
Azhar S. S., Liew A. G., Suhardy D., Hafiz K. F. and Hatim M. D. I. (2005), Dye
removal from aqueous solution using adsorption on treated sugarcane bagasse.
American Journal of Applied Sciences 2 (11) 1499 – 1503, (2005).
Brown N.W. , Roberts E.P.L. , Garforth A. A. , and Dryfe R. A. W. (2004 a),
Treatment of Dye House Effluents Carbon Based Adsorbent Using Anodic Oxidation
Regeneration, Water Science and Technology, VOL. 49, No. 4, PP. 219-225.
Brown N.W., Roberts E.P.L., Chasiotis A., Cherdron T., and Sanghrajaka N. (2004
b), Atrazine Removal Using Adsorption and Electrochemical Regeneration, Water
Research 38, 3067-3074.
Brown N.W. , Roberts E.P.L. , Garforth A. A. , and Dryfe R. A. W. (2004 c),
Electrochemical Regeneration of A Carbon Based Adsorbent Loaded With Crystal
Voilet Dye, Electrochimica Acta 49 (2004) 3269-3281.
Brown N.W. (2005), Adsorption and Electrochemical Regeneration for Waste Water
Treatment, Ph D Thesis, Submitted to the University of Manchester, School of
Chemical Engineering and Analytical Sciences.
Brown N.W. (1995), Development of a Cleaner Process for the Manufacture of
Exfoliating Graphite. Dissertation submitted as part of the Master of Science degree
in Integrated Pollution Management. The University of Manchester, Institute of
Science and Technology, Manchester.
Kannan N. and Murugaval S. (2008), Comparative study on the removal of acid violet
by adsorption on various low cost adsorbents. Global NEST Journal, Volume 10, No.
3, pp 395 – 403, (2008).
24
30. Sivaraj R., Namasivayam C. and Kadirvelu K. (2001), Orange peel as an adsorbent
in the removal of Acid Violet 17 (acid dye) from aqueous solutions. Waste
management 21, (2001) 105 – 110
Thinakaran N., Baskaralingam P., Pulikesi M., Panneerselvam P., and Sivanesan S.
(2007), Removal of Acid Violet 17 from aqueous solutions onto activated carbon
prepared from sunflower seed hull. Journal of hazardous materials 151 (2008) 316 –
322.
25
31. 2.2 Using Intermittent Sand Filter for Grey Water
Treatment: Case Studies in Jordanian Rural
Communities
Almoayied K. Assayed
University of Surrey, Guildford, Surrey GU2 7XH Tel. 07879545917 Fax.
01483686671; a.assayed@surrey.ac.uk
KEYWORDS: Grey water, grey water treatment techniques, intermittent sand filter,
Jordanian rural communities
ABSTRACT
This paper aims to present case studies of onsite grey water treatment in a small
rural community in Jordan and student halls of residence using septic tanks followed
by intermittent sand filter. These case studies were implemented by the
Environmental Research Centre in the Royal Scientific Society in Jordan during the
period 2006-2009 and funded by International Development Research
Centre/Canada.
Grey water is commonly defined as wastewater without input from toilets and kitchen.
In other words, grey water is a wastewater from laundries, showers and hand basins.
Separation of domestic wastewater at source is wide spread practice in many of the
rural communities in Jordan; black water from toilets is discharged to cesspools and
septic tanks, while grey water is directly discharged to the environment or used for
irrigation without treatment. Grey water comprises about 30% of the total household
water use, and it can be considered an alternative that provides non-potable water
for household usage, and thus reduces the per capita water use by 50%. For this
reason it provides an attractive and sustainable low cost water source especially in
arid and semiarid areas due to general water scarcity and the fluctuations in the
rainfall patterns. Treatment technologies for making grey water safe for indoor use or
for irrigation are many and diverse and they vary from simple systems in single
households to more advanced systems for large scale reuse. Course filtration with
disinfection represents the most common technology used for grey water treatment in
many places in the world. Septic tank followed by sand filter is an attractive
alternative for grey water treatment. Septic tanks act as a settling basin for the
wastewater. Heavy materials settle down to the bottom of the tank. Water, other
26
32. liquids and suspended solids are found above the sludge. Soap and grease form a
floating scum layer. Intermittent sand filters provide unsaturated downward flow of
wastewater through mineral sand, so as to provide biodegradation or decomposition
of wastewater constituents by bringing the wastewater into close contact with a well
developed aerobic biological community attached to the surfaces of the filter media.
One pilot intermittent sand filter was designed and operated in one rural village in
Jordan during 2006-2008. A 1 m3 septic tank followed by 6m2 intermittent sand filter
of 1m in depth were used to treat an average flow of 150L/Day of grey water effluent
from a single household in “Abu Al Farth” Village in the Badia of Jordan. The raw
greywater had a total BOD5 of about 1149mg/L, total suspended solids TSS of
606mg/L, COD of 1952mg/L and E.coli of 9400MPN/100mL. The treatment efficiency
of BOD5, COD, total suspended solids and E.coli were 95%, 93%, 95% and 90%
respectively. The treated grey water had an average BOD5 of 59 mg/L, TSS of 31
mg/L, COD of 161 mg/L and E.coli of 227 MPN/100mL. The quality of treated grey
water complies with the Jordanian Standards JS (893/2006) for reclaimed
wastewater reuse for restricted irrigation.
Another sand filter unit was designed and operated to treat 4m3/day of grey water
produced from student accommodation in one Jordanian university. The filter was
monitored during the period 2007-2009. The surface area of the filter was 32 m2 with
1m depth. The raw grey water had a total BOD5 of about 127 mg/L, total suspended
solids TSS of 43 mg/L, COD of 233 mg/L and E.coli of 45440 MPN/100mL. The
treatment efficiency of BOD5, COD, total suspended solids and E.coli were 94%,
92%, 98% and 98% respectively. The treated grey water for both filters were being
used for irrigation and agricultural land development which, in turn, improved land
production and crop quality.
The study concluded that low consumption rates of water in the household results in
high pollution loads of the generated grey water, and this pollution requires the grey
water to be treated before use both to conserve environment and to protect health.
The composition and characteristics of grey water vary significantly and are very
dependant on the practices of the household's inhabitants. Septic tank collection
followed by intermittent sand filter was found to be a very effective treatment system
for both low-level and high-level polluted grey water with overall removal efficiency of
more than 90%. However, failure of the sand filter due to clogging is the main
concern for the long term operation of the treatment system.
27
33. 2.3 Application of Natural and Modified Materials for
Treatment of Acid Mine Drainage
Bogush A.A.*1, Voronin V.G.**, Galkova O.G.*, Ishuk N.V.*
* Institute of Geology and Mineralogy SB RAS, Koptyug Pr. 3, 630090 Novosibirsk,
Russia, annakhol@gmail.com
** Planeta-Ra Ltd., Lazurnay str. 4/3, 630133 Novosibirsk, Russia,
woronin54@mail.ru
1
Details for contact author: annakhol@gmail.com, tel. 07826272095
KEYWORDS: acid mine drainage, pollution, AMD treatment
ABSTRACT
A huge amount of waste has accumulated in the world during the last century as a
result of industrial activity. The waste products of the ore mining and processing
industry are dangerous because of the high concentration of heavy metals and low
pH. For example, sulphide tailings are oxidized by atmospheric oxygen forming acid
mine drainage (AMD) with high concentrations of SO42-, Fe, Zn, Cu, Cd, Pb and
other elements. The treatment of acid mine drainage is a critical problem at present.
Various agents (carbonate rocks, activated carbon, zeolite, iron (III) hydroxide,
cellulose, etc.), different protective screens (Sergeev et al., 1996; Doncheva and
Pokrovskiy, 1999; Maximovich and Blinov, 1994; Maximovich et al., 1999; Kovalev et
al., 2000; Zosin et al., 2004; etc.), and microbial populations (Benner et al., 2000;
Sandstrom and Mattsson, 2001; Foucher et al., 2001; Kim et al., 2000) are used to
minimise the technogenic influence of the mining and processing industry. In the
given investigation, new methods of AMD treatment have been developed on the
basis of natural (clay, peat, limestone, etc.) and modified materials (peat-humic
agent (PHA), organic-mineral complex, etc.). The combination of field, experimental,
mineralogical, physical and chemical research has been applied for solving this
problem. Various methods, such as chemical methods, AAS, IRS, XRD and SEM,
were used for this research. Laboratory investigations were carried out in the
Analytical Centre of the Institute of Geology and Mineralogy of Siberian Branch of
Russian Academy of Sciences. The chemical compounds of technogenic water and
solid wastes were investigated in detail. Methods for modification of natural materials
were utilised to intensify sorption properties of clay minerals and peats. Methods of
acid mine drainage neutralisation and decreasing contaminant concentration were
offered using the natural and modified materials. For example, peat-humic agent has
28
34. been produced from peat from the “Krugloe” deposit (Novosibirsk region, Russia) by
mechanical, chemical and thermobaric modifications. This agent has more humic
acids and functional groups, especially carboxyl, than peat. It is a good sorbent for
potentially toxic elements and can alkalise acid and subacid drainage waters. In this
paper we describe the use of peat-humic agent (PHA) for the treatment of acid mine
drainage. The development of the new scheme was based on investigations of
humic acid properties (Aleksandrova, 1980; Orlov and Osipova, 1988; Orlov, 1990;
Varshal et al., 1993; Bannikov, 1990; Holin, 2001; etc.) and our preliminary research
of sulphide tailings (Bogush and Lazareva, 2008; Bogush and Androsova, 2007;
Bogush et al., 2007). The PHA was used to modify kaolinite clay in order to create
organic-mineral complex. Clay, modified by microaddition of PHA, has a sorption
capacity 1.7-2 times higher than natural clay and can sorb metals in extended range
of pH from 5 to 8. Also, we propose a method of metal extraction from AMD which is
economically and ecologically preferable than simple AMD treatment. These
methods will reduce the hazardous effect of mine waste on environment.
This work was supported by RFBR grant (#03-05-64529 and #06-05-65007) and
interdisciplinary project SB RAS (#31).
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Aleksandrova L.N. (1980) Organic substance of soil and processes of its
transformation. Publishing house of Science, Moscow.
Benner S.G., Gould W.D., Blowes D.W. (2000) Microbial populations associated with
the generation and treatment of acid mine drainage. Chemical Geology, 169, 435-
448.
Bogush A.A. and Androsova N.V. (2007) Ecogeochemical condition of river system
of S. Talmovaya - Talmovaya - S. Bachat - Bachat - Inya (Kemerovo region).
Ecology of industrial production, 1, 8-16.
Bogush A.A. and Lazareva E.V. (2008) Migrational properties of elements in the
sulfide tailings and technogenic bottom sediment. Goldschmidt Abstracts 2008- B,
Geochimica et Cosmochimica Acta, Volume 72, Issue 12, Supplement 1, Pages A
92.
Bogush A.A., Letov S.V., Miroshnichenko L.V. (2007) Distribution and speciation of
heavy metals in drainage water and sludge pond of the Belovo zinc plant (Kemerovo
region). Geoecology, 5, 413-420.
29
35. Doncheva A.V. and Pokrovskiy S.G. (1999) Fundamentals of ecological production
engineering. Publishing house of the Moscow State University, Moscow.
Foucher S., Battaglia-Brunet F., Ignatiadis I., Morin D. (2001) Treatment by sulfate-
reducing bacteria of Chessy acid-mine drainage and metals recovery. Chemical
Engineering Science, 56, 1639-1645.
Holin J.V. (2001) Humic acids as main complexion substances. Journal
Universitates, 4, 21-25.
Kim B.H., Chang I.S., Shin P.K. (2000) Biological treatment of acid mine drainage
under sulphate-reducing conditions with solid waste materials as substrate. Water
Research, 34, 1269-1277.
Kovalev I.A., Sorokina N.M., Tsizin G.I. (2000) Selection of effective sorbent for
dynamic concentration of heavy metals from solution. Herald of the Moscow State
University, 41(5), 309-314.
Maximovich N.G. and Blinov S.M. (1994) The use of geochemical methods for
neutralization of surroundings aggressive to underground structures. In Proc. 7th Int.
Congress Ass. of Engineering Geology, Lisbon, 3159-3164.
Maximovich N.G., Kuleshova M.L., Shimko T.G. (1999) Complex screens to protect
groundwater at sludge sites. In Proc. Conference on Protection of groundwater from
pollution and seawater intrusion. Bari, 14.
Orlov D.S. (1990) Humic acids of soil and general theory of ulmification. Publishing
house of the Moscow State University, Moscow.
Orlov D.S., Osipova N.N. (1988) Infra-red spectrums of soil and soil components.
Publishing house of the Moscow State University, Moscow.
Bannikova L.A. (1990) Organic substance in hydrothermal ore formation. Publishing
house of Science, Moscow.
Sandstrom A. and Mattsson E. (2001) Bacterial ferrous iron oxidation of acid mine
drainage as pre-treatment for subsequent metal recovery. International Journal of
Mineral Processing, 62, 309-320.
Sergeev V.I., Shimko T.G., Kuleshova M.L., Maximovich N.G. (1996) Groundwater
protection against pollution by heavy metals at waste disposal sites. Wat. Sci. Tech.,
34(7-8), 383-387.
30
36. Varshal G.M., Velyuhanova T.K., Koshcheeva I.J. (1993) Geochemical role of humic
acids in migration of elements. In Proc. Conference on Humic substances in
biosphere, 97-117.
Zosin A.P., Priymak T.I., Avsaragov H.B., Koshkina L.B. (2004) Laboratory research
of cementing materials for protective barriers on basis of metallurgical slag, 4, 342-
345.
31
37. 2.4 Exploring the Potential of Agricultural Constructed
Wetlands to Mitigate Diffuse Pollution
Deasy C.1*, Quinton J.*, Stoate C.** and Bailey A.P†
* Lancaster Environment Centre, Lancaster University, Lancaster, LA1 4YQ
** Game & Wildlife Conservation Trust, Loddington House, Main Street, Loddington,
Leicestershire, LE7 9XE
†Department of Agriculture, University of Reading, Reading, RG6 6AR
1
Contact author. Tel: 01524 593971; fax: 01524 593985; email: c.deasy@lancs.ac.uk
KEYWORDS: Diffuse pollution, agriculture, mitigation, constructed wetland
ABSTRACT
Pollution from diffuse agricultural sources is currently of concern for water quality,
with recent Defra figures suggesting that agriculture is responsible for 70% of
sediment, 60% of nitrate, and 25% of phosphorus inputs into rivers and lakes. In the
UK, in-field mitigation options such as minimum tillage have been found to be
effective at reducing sediment and nutrient loss in surface runoff (Deasy et al., 2009).
In-field approaches are unable to tackle pollutants which do manage to reach ditches
and streams, for example through sub-surface flow pathways such as artificial
drainage systems. However, edge-of-field mitigation options, such as constructed
wetlands, which can tackle pollution from drain outfalls and ditches have potential for
tackling diffuse pollution from all runoff pathways. Constructed wetlands have been
well-researched outside the UK, particularly in Norway, where they are now used as
an option within agri-environment schemes (Ulén et al., 2007), but very little data are
available in relation to their potential for use within UK landscapes. The Defra-funded
MOPS2 project (2008-2013) aims to make recommendations on the use of
constructed wetlands for diffuse pollution control by creating and monitoring ten of
these features in agricultural landscapes across the UK. The effectiveness of a
number of constructed wetland designs will be determined over the course of the
project.
Three types of constructed wetland are being trialled, shallow single ponds, shallow
paired ponds, and deep and shallow paired ponds. Shallow ponds are 0.5 m deep,
and act as filters to trap sediment and associated nutrients. The shallow depth
32
38. means that emergent macrophyte vegetation can grow, which can help trap sediment
and nutrients and prevent sediment resuspension. Deep ponds are around 1.5 m
deep, and act as sedimentation traps, which may allow increased storage of
sediment. Paired ponds also have the potential to increase the effectiveness and
longevity of constructed wetlands. In addition, three sizes of wetland are being
tested, a ‘medium size’ which represents 0.05% of the catchment area or 50 m2 for
each 10 ha, a ‘small size’ which is half this, and a ‘large size’ which is double this.
The ‘medium size’ wetland is the size of wetland shown to be effective n Norway,
where it is the size required for subsidised state funding. The constructed wetland
systems in this project are designed so that the flow length is maximised, with a
width:length ratio of around 1:5. Where systems are shorter, barriers are used to
route flow through the ponds. As these systems are not designed to take heavily
polluted runoff from point sources, ponds are currently unlined. Risk of pollution
losses to groundwater will be assessed in a later part of the project.
Six constructed wetlands have been built to date at three sites on different soil types
in Cumbria and Leicestershire (Table 1), with different designs of wetland mixed
between the sites. A further four wetlands are to be implemented in 2010, at
locations to be confirmed. Flow and sediment particle transport through the
constructed wetlands is measured at wetland inlets and outlets through continuous
monitoring of flume water levels and turbidity, while collection of water samples
during storms allows assessment of sediment and nutrient transfer into and out of the
wetland. Assessment of sedimentation rates and sediment sampling will also be
carried out in the course of the project. The data will be used to generate wetland
sediment and nutrient budgets and calculate sediment and nutrient load reductions
and wetland effectiveness.
As the constructed wetlands are expected to mature and vegetate naturally over
time, some maintenance is likely to be required in order to prevent the wetland
becoming clogged with vegetation, remove stored sediment, and prevent the wetland
becoming a source for pollution rather than a sink. Previous work in Scandinavia has
focused on the effectiveness of new constructed wetlands for pollution control (e.g.
Braskerud et al., 2005) but there is limited information available relating to effects of
wetland maturation or on the level of maintenance required over time. It is expected
that a wetland may need to be dredged after five to ten years, depending on the size
of the wetland and the sediment load. The sediment in the retention ponds can be
considered a nutrient resource, and samples will be analysed in order to assess the
fertiliser value of the dredged sediment for farmers.
33
39. Constructed wetlands are relatively inexpensive to build, but real farm-scale costs will
be assessed within the MOPS project once all sites are completed. In addition,
farmer questionnaires and focus groups will also be used to acquire farmer feedback
and assess likeliness of uptake by farmers of all in-field and edge-of-field mitigation
options explored. In this paper we explain the constructed wetland designs being
trialled, discuss issues relating to their implementation, and present some early
results of the project.
REFERENCES
Braskerud, B., Tonderski, K. S., Wedding, B., Bakke, R., Blankenberg, A.-G. B.,
Ulen, B. and Koskiaho, J. (2005). Can constructed wetlands reduce the diffuse
phosphorus loads to eutrophic water in cold temperate regions? Journal of
Environmental Quality, 34, 2145-2155.
Deasy, C., Quinton, J. N., Silgram, M., Bailey, A. P., Jackson, B. and Stevens, C. J.
(2009). Mitigation Options for Sediment and Phosphorus Loss from Winter-sown
Arable Crops. Journal of Environmental Quality, 38, 2121-2130.
Ulén, B., Bechmann, M., Fölster, J., Jarvie, H. P. and Tunney, H. (2007). Agriculture
as a phosphorus source for eutrophication in the north-west European countries,
Norway, Sweden, United Kingdom and Ireland: a review. Soil Use and Management,
23, 5-15.
34
40. Table 1. Location, design, sizes, sources and status of constructed wetlands used as
edge-of-field mitigation options for diffuse pollution within the MOPS2 project.
Contributing Approx
Area Runoff
Site Design Area Size Dimensions Status
(m2) Source
(ha) (m)
Shallow Large Finished
1 paired 10 (0.1% 100 7 x 15 Ditch autumn
ponds area) 2008
Medium
Deep &
(0.05% Finished
shallow
1 4 area) 20 2 x 10 Drain autumn
paired
(0.025% 2009
ponds
area)
Shallow Small Finished
Surface
1 single 9 (0.025% 22 2 x 11 autumn
Runoff
pond area) 2009
Shallow Large Finished
Surface
2 paired 20 (0.1% 190 33 x 6 autumn
Runoff
ponds area) 2009
Delayed
until June
Deep &
Small 2009 (due
shallow
2 50 (0.025% 125 25 x 5 Stream to EA
paired
area) Land
ponds
Drainage
Consents)
Shallow Medium Finished
2 single 10 (0.05% 50 17 x 3 Drain autumn
pond area) 2009
Deep &
Large Finished
shallow
3 30 (0.1% 320 40 x 8 Drain autumn
paired
area) 2009
ponds
Site 1 = Loddington, Leicestershire, site 2 = Crosby Ravensworth, Cumbria, site 3 =
Plumpton, Cumbria
35
41. 2.5 Recovering Resources and Reducing the Carbon
Footprint: a Better Way to Deal with Wastewater
Screenings
N.J. Horan*, L.S. Cadavid+*1, N. Wid*
*
School of Civil Enginnering, University of Leeds, United Kingdom
+
Area de Ingeniería, Universidad Nacional de Colombia, Palmira, Colombia
1
Luz Stella Cadavid, Assistant Professor, Universidad Nacional de Colombia,
Palmira, Colombia; PhD student, University of Leeds, United Kingdom; Fax: (44)
01133432265; Email: cnlscr@leeds.ac.uk
KEYWORDS: Wastewater Screenings, carbon footprint, anaerobic digestion,
methane potential, nutrients recovery
ABSTRACT
Currently the wastewater sector faces a big challenge to maintain and improve
effluent quality while reducing carbon emissions and energy consumption in all its
processes. One material which is a by-product of the treatment process and for
which little attention has been paid, is wastewater screenings which are recovered
from the screens that are found at the inlet to all treatment plants. There is no ideal
disposal method for this waste and in the UK they are disposed of primarily to landfill
with a smaller fraction incinerated. As a result the potential CO2e emitted to the
atmosphere is around 1.8 tonnes per tonne of dry screenings disposed.
The UK water industry is responsible for emitting around 5 million tonnes of CO2 per
annum and currently accounts for 3% of the nation’s total energy demand. It is the
third most energy intensive sector. Therefore given the current urgent need for
reducing carbon emissions, the sector has a key role to play. Innovative solutions are
needed to reduce emissions, particularly in the treatment of wastewater, because this
area is responsible for about 56% of total sector emissions. One solution that already
contributes to the reduction of CO2 emissions and which offers the alluring possibility
of energy self-sufficiency in the wastewater treatment is the application of anaerobic
digestion. If this could be extended to include wastewater screenings it would not
only reduce more than 50% of the CO2 emissions caused when screenings are
landfilled, but also produce a significant amount of renewable energy in the form of
methane.
36
42. In addition to methane production, anaerobic digestion of wastewater screenings
may also provides the opportunity to recover the nutrients phosphorus and nitrogen.
As readily recoverable phosphorus is anticipated to be exhausted in 50 – 100 years,
it is important to identify opportunities for recycling these nutrients from other
sources. This paper will show that screenings have potential to yield 0.45 m3
methane/m3 VS applied and with the release of up to 13% phosphate and 60% of
nitrogen in the liquid phase when digested under mesophilic conditions. However the
engineering design of the digester is crucial in order to handle this difficult waste.
37
43. 2.6 Natural Wastewater Treatment Systems for
Nitrogen Control and Recovery
Camargo-Valero, M. A.
School of Civil Engineering, University of Leeds, Leeds LS2 9JT. Tel. +44 (0)113
3431957; Email: M.A.Camargo-Valero@leeds.ac.uk
KEYWORDS: Natural wastewater treatment, nitrogen control, waste stabilization
ponds
ABSTRACT
The increasing accumulation of reactive forms of nitrogen in the biosphere is largely
attributed to the industrial production of nitrogen fertilizers, which has increased
almost tenfold in the past seven decades. Ultimately, water bodies will receive the
excesses of nitrogen loads after they have fed intensive agriculture and animal
production systems for supplying food to an exponentially growing world population
and supporting an emerging fuel-from-crop industry. Wastewater treatment works
(WWTW) contribute to mitigate negative environmental impacts due to the discharge
of reactive nitrogen species into receiving water bodies by using nitrification-
denitrification processes; however, only 5% of the total volume of wastewater
receives tertiary treatment (nutrient control) worldwide. The global commitment for
carbon footprint reduction in the water industry is driving the development of new,
and adaptation of existing, low-carbon/ carbon-neutral technologies that will help to
meet nutrient control targets in WWTW. Natural wastewater treatment systems like
Waste Stabilisation Ponds (WSP) may play an important role to achieve such targets
and therefore, it is important to improve our understanding about the dynamics of
nitrogen species in WSP. This work reveals the main nitrogen transformation
pathways and removal mechanisms in WSP in the UK, and presents the feasibility of
implementing Natural Wastewater Treatment systems for nutrient control and
recovery in rural and small communities.
38
44. 3a & 3b. Monitoring, Ecosystems &
Health
3.1 Identification of nitrate sources in a chalk water
supply catchment in Yorkshire, UK
Grayson, R.1, Kay, P. 1 and Nixson, N. 2
1
School of Geography, University of Leeds, Leeds, LS2 9JT, UK.
2
Yorkshire Water Services Ltd, Western House, Western Way, Bradford, BD6 2LZ,
UK.
KEYWORDS: Diffuse pollution; groundwater; surface water
ABSTRACT
Diffuse nitrate pollution from agriculture remains problematic from a water quality
perspective. Nitrate concentrations within the River Hull, East Yorkshire, UK, have
increased gradually since the 1970s and are now routinely close to the EU statutory
limit of 11.3 mg N l-1. Fortnightly monitoring of eight surface water sites and three
groundwater sites was undertaken over a one year period to identify the main
sources of nitrate within the R. Hull catchment. Nitrate was found to be high
throughout the catchment, being highest in the groundwater samples in the north,
with surface water sites showing a slight decrease downstream as the contributions
from surface runoff and the lower less polluted part of the aquifer increase
downstream. Given that groundwater is the dominant source of nitrate, catchment
management is unlikely to reduce nitrate pollution in the R. Hull in the short to
medium term due to the residence time of the aquifer (estimated to be decades);
however intervention now may reduce nitrate in the longer term.
39
45. 3.2 Impacts of Artificial Drainage and Drain-blocking
on Peatland Stream Ecosystems
Ramchunder, S.*, Brown, L. and Holden, J.
School of Geography, University of Leeds, Leeds, LS2 9JT
*Email: geosjr@leeds.ac.uk
KEYWORDS: Stream benthic macroinvertebrates; catchment-scale remediation
ABSTRACT
Peatlands are important global systems however; many have been intensively
managed through artificial drainage and drain-blocking. This study discusses the
impacts of these management interventions on stream benthic macroinvertebrates
across northern England compared with intact peatland systems. Results indicate
compositional shifts in artificially drained systems, while species compositions in
drain-blocked sites were typically similar to levels in intact systems. Therefore, drain-
blocking appears to be an effective catchment-scale remediation strategy.
40
46. 3.3 Distribution and Sources of Polycyclic Aromatic
Hydrocarbons in the Mediterranean Lebanese
Seawater
A. Kouzayha*, M. AL Iskandarani*, B. Nsouli*, H. Budzinski** and
F. Jaber*1
*Analysis of Pesticides and Organic Pollutants Laboratory (LAPPO), Lebanese
Atomic Energy Commission (LAEC), National Council for Scientific Research
(CNRS), Beirut, Lebanon
**Université Bordeaux 1, CNRS, ISM–LPTC–UMR 5255 (Laboratory of Physico- and
Toxico-Chemistry), 351 Cours de la Libération, 33405 Talence, France
1
Corresponding author. Farouk Jaber, Lebanese Atomic Energy Commission, P.O.
Box: 11-8281 Riad El Solh 1107 2260 Beirut, Lebanon. Tel.: +961 1 450811 (303);
fax: +961 1 450 810. Email address: fjaber@cnrs.edu.lb.
KEYWORDS: Polycyclic Aromatic Hydrocarbons (PAHs) analysis; Mediterranean
Lebanese surface seawater; Solid Phase Extraction (SPE); Gas Chromatography–
Mass Spectrometry (GC–MS).
ABSTRACT
Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental
contaminants and have been extensively studied due to their toxicity, carcinogenicity,
mutagenicity and bio accumulative effects in aquatic organisms (3,4,5,9). Several
factors influence the presence and distribution of PAHs in the marine environment,
such as petroleum contamination due to large oil spills accidents and oil discharges
from ships, fallout from air pollution and terrestrial runoff (2,11,17). The Lebanese
coastal zone that stretches to about 225 km of length with about nearly 2.6 million
people resident there, presents 13 pollution hot spots from north to south according
to the European Environment Agency EEA (7). Domestic and industrial wastes are
discharged directly on the shore and into the sea in the major coastal cities. Maritime
transport is also a major source of petroleum hydrocarbon pollution along the
Lebanese coastline. In addition, about 15000 tons of heavy fuel oil have been spilled
into the Mediterranean Lebanese sea after the bombing of the Jiyeh power plant,
located at the south of the capital Beirut, during the war in July 2006 (3).
41
47. The aims of this work were to study the distribution of 15 PAHs (Table 1), classified
as priority pollutants by the United States Environmental Protection Agency US EPA
(11), for the first time in the surface seawater along the Lebanese coast in the
eastern part of the Mediterranean basin, and to try to identify their sources.
1. SAMPLING, EXTRACTION, ANALYSIS AND QUALITY CONTROL
This study was carried out between January 2009 and April 2009. Water samples
were collected in 2.5 L dark glass bottles from 5 sites located in north Lebanon
(Tripoli Port, Tripoli Mina, Kalamoun, Chekka and Batroun Selaata), 3 sites located in
the capital Beirut (Saint-George Port, Beirut Ramle Bayda and Beirut Manara) and 7
sites located in south Beirut and in south Lebanon (Damour, Jiyeh, Sayda, Tyr
Murex, Tyr Katolik, Tyr Christians and Tyr Khiyam). Figure 1 shows the Lebanese
coast map and the sampling sites.
Figure 1. Map of the Lebanese coast and the selected sampling sites
Water samples were vacuum filtered through a Whatman GF/F filter (0.7 μm
porosity). Each seawater sample (1 L) was preconcentrated by solid phase extraction
(SPE) using CHROMABOND® C18 ec polypropylene columns (3 ml, 200 mg) from
Machery-Nagel with a flow rate of 2-3 ml/min. The C18 cartridges were pre-
conditioned and activated with 2 x 3 ml of methylene choride (DCM), 3 ml methanol
and finally 3 ml of distilled water before sample percolation. The SPE system used
was Vac Elut 20 from Varian with Visiprep™ Large Volume Sampler from Supelco.
After drying the SPE sorbent under high vacuum for 1 hour, they were eluted by 9 ml
DCM under low vacuum. The DCM collected volume was reduced under a stream of
nitrogen at 50°C to a volume less than 100 μL.
42
48. Table 1. 15 PAHs analysed and 3 deuterated PAHs as internal standards, their
abbreviations, retention times and diagnostic m/z ions in SIM mode of GC/MS
Compound Abbreviation tR m/z Internal Standard tR m/z
Acenaphthylene ACY 18.489 152
Acenaphthene ACP 19.364 154
Phenanthrene
Fluorene FLR 21.714 166 27.313 188
D10
Phenanthrene PHE 27.446 178
Anthracene ANT 27.446 178
Fluoranthene FLT 35.819 202
Fluoranthene D10 35.706 212
Pyrene PYR 37.294 202
Benzo(a)Antharcene BaA 46.506 228
Chrysene CHR 46.772 228
Benzo(b)Fluoranthe BbF 54.155 252
ne
Benzo(k)Fluoranthe BkF 54.324 252
ne
Chrysene D12 46.603 240
Benzo(a)Pyrene BaP 56.106 252
Indeno(1,2,3- IcP 62.813 276
cd)Pyrene
Dibenzp(a,h)Anthrac DhA 63.182 278
ene
Benzo(ghi)Perylene BgP 64.091 276
43
49. Figure 2. Chromatogram of 15 PAHs
The analysis of samples was performed in an Agilent Gas-Chromatographic GC
6890N coupled to a Mass-Spectrometry detection MSD 5975 Inert utilizing high pure
helium as carrier gas, an HP- 5MS column and the following separation conditions:
60°C for 2 min to 155°C at 5°C/min, then 155°C for 2 min to 280°C at 3°C/min,
splitless injection mode, temperature of injector was set at 240°C. All samples were
analyzed in Single Ion Monitoring (SIM) mode for quantification as indicated in Table
1. Internal standard calibration was used for quantification of the extracts. The
deuterated surrogate standards were added to both samples and spiked waters prior
to the extraction. Surrogate and internal standards for each group of PAHs are
shown in Table 1. The chromatogram of the 15 PAHs standards and 3 deuterated
PAHs is presented in Figure 2.
The validation of chemical analysis were performed via a recovery determination of a
blank water sample spiked with a known amount of PAHs (1 μg L-1) and processed
according to the described method. The yields of recovery and the concentrations in
samples were calculated according to concentrations of all PAHs in Standard
Reference Solution from ChemService (Cat.PPH-10RPM) with concentration 100
mg/L of each. The recoveries of different PAHs obtained (Figure 3) ranged between
70% for Acenaphthylene (ACY) and 106% for Benzo(a)Anthracene (BaA). Laboratory
analytical precision was determined by making replicate analysis to ascertain
reproducibility. The standard deviations of PAHs recovery calculated in spiked tests
were less than 20% (Figure 3). The average standard deviation was about 12%. The
limits of detection (LOD) of the individual PAHs were calculated as signal to noise
ratio 3:1 and ranged from 0.05 ng/L for Phenanthrene (PHE) and 0.1 ng/L for
Dibenzo(a,h)Anthracene D(a,h)A. Intensive efforts were made to avoid contamination
and blank cartridges were made with all series of extraction.
44
50. Figure 3. Mean recovery (%) and standard deviation SD (%) of individual PAHs for
replicates (n = 10)
2. RESULTS AND DISCUSSION
The total concentrations (the sum of all the 15 PAHs) and the concentration of
individual PAHs determined for all sites are presented in Figure 4. ∑PAHs values in
the surface seawater were found in the range of 25-50 ng/L at the most polluted
sites, and in the range of 3-15 ng/L at the other sites. The relatively high
concentrations observed for Beirut Saint George Port are linked to the amount of
boat traffic and the constant petroleum spills in the small closed port. High PAHs
concentrations found in Sayda city might be associated with the discharge of
domestic wastewater and solid wastes in this area located in south Lebanon
compared to the other sites.
Although intercomparison studies of PAH analysis are relatively poorly developed in
aqueous samples, the values measured can be considered as relatively moderate
levels in water in comparison with the few results reported for marine systems around
the Mediterranean (0.5-2.2 ng/L in the open western Mediterranean (4) and 50 ng/L
in southeastern Mediterranean (6).
PAHs composition (Figure 5) was dominated by three- and four-rings compounds.
The low presence of heavy PAHs of five- and six- rings is indicative of the strong
binding of these PAHs to the dissolved or solid matters and their low seawater
solubility. The study of the composition of PAH mixtures can provide useful
information regarding the origin of these compounds. This predominance of the low
molecular weight PAHs, common to all sites, is characteristic of uncombusted fossil
fuel residues (13). In sites of Batroun-Selaata, Sayda and Tyr-Murex, the presence of
45
51. heavy PAHs with higher percentages than other sites indicates an additional pyrolytic
source of PAHs.
Figure 4. Concentration of the sum of the 15 PAHs in seawater (ng/L)
Figure 5. Percentage of individual PAHs values in samples
Diagnostic interpretation of the distribution of certain PAHs in seawater such as
PHE/ANT and FLT/PYR ratios has been used to distinguish the possible pyrogenic or
pyrolytic sources of pollution in the sea. Some characteristic values for molecular
indices used to investigate PAHs sources are given in Table 2.
46
52. Table 2. Characteristic values of molecular indices for pyrolytic and petrogenic
origins of PAHs
PHE/ FLT/ ANT/(AN FLT/(FLT CHR/ BaA/ (PHE/AN
ANT T+PHE) +PYR) BaA T)/
PYR CHR
(FLT/PYR
)
Pyrolytic < 10 >1 > 0.1 > 0.5 <1 > 0.9 0-10
origin
Petrogeni > 10 <1 < 0.1 < 0.5 >1 ≤ 0.4 > 10
c origin
Reference 15 14 15 14 9 9 1
Based on the ratios of PHE/ANT plotted against values of FLT/PYR in Figure 6 and
on the ratios of CHR/BaA plotted against values of FLT/PYR in Figure 7, it can be
seen that seawater was mainly contaminated by petrogenic PAHs in some sites
(Saint George-Port, Beirut Manara and Beirut Ramle Bayda) and by pyrolytic PAHs
in other sites (Sayda, Tyr Murex). In addition, it was also observed that the
occurrence of PAHs may originate from both pyrolytic and petrogenic sources in
some sites (Jiyeh, Sayda, Kalamoun, Tyr Christians and Tyr Khiyam).
Figure 6. Values of PHE/ANT plotted against values of FLT/PYR
47