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Water quality 2010abstract booklet

  1. 1. Water Quality 2010: Proceedings of the conference 23 – 24 June 2010 Weetwood Hall Hotel, Leeds Conference Proceedings
  2. 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. 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. 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. 5. Delegate List 109 Conference Secretariat & Committee 111
  6. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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 g1. 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 g1. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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). REFERENCES 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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