SILVIA GIULIANI – MAURO FRIGNANI
Towards Environmental Quality Assessment in a Developing Area The Bac Giang Province bordering the Cau River (Northern Vietnam)
Proceedings of the workshop Environmental Quality in the Province of Bac Giang and the Cau River Basin. Perspectives for the improvement of monitoring activities and methods Hanoi, August 27th, 2013.
Towards Environmental Quality Assessment in a Developing Area The Bac Giang Province bordering the Cau River (Northern Vietnam) Proceedings of the workshop Environmental Quality in the Province of Bac Giang and the Cau River Basin. Perspectives for the improvement of monitoring activities and methods Hanoi, August 27th, 2013.
Editors: Silvia Giuliani Mauro Frignani
Published with the support of:
NGO Civil Volunteer Group (GVC) Via dell’Osservanza 35/2, 40136 Bologna, Italy
© Giraldi Editore, 2014 Tutti i diritti riservati
[email protected] [email protected] www.giraldieditore.it ISBN 978-88-6155-586-0
Table of Contents Introductory note to the volume ................................................................. 1 R. Mattei
Presentation of the Project “Promotion of environmental protection in the Viet Yen, Yen Dung and Hiep Hoa districts in the Bac Giang Province, Vietnam”: implementation, strategies and results ................... 3 M. Romanelli
Water Quality Trends of the Cau River Basin from 2008 to 2012 ......... 19 Nguyen Van Thuy, Nguyen Huu Thang, Nguyen Duc Thanh, Nguyen Hong Hanh
Promotion of Environmental Quality in the Districts of Viet Yen, Yen Dung and Hiep Hoa in the Bac Giang Province, Vietnam: sediment and soil samples for environmental quality assessment ......... 33 S. Romano, S. Giuliani, L. G. Bellucci, M. Frignani
Methods used for the determination of contaminants in selected soils and sediments of south-east Bac Giang Province (Vietnam) ......... 47 S. Zambon, C. Turetta, M. Vecchiato, R. Piazza, S. Giuliani, S. Romano, G. Tranchida, L. G. Bellucci, F. D’Agostino, C. Barbante, M. Frignani
Distribution and risk assessment of minor and trace elements in soils and sediments from the Cau River Basin (Bac Giang Province, Northern Vietnam) ..................................................................................... 59 C. Turetta, F. Corami, S. Romano, S. Giuliani, L. G. Bellucci, M. Frignani, C. Barbante
PCBs, PBDEs, PCDD/Fs, chlorinated pesticides and hydrocarbons in soils and sediments from the Bac Giang Province and the Cau River (northern Vietnam).......................................................................... 77 R. Piazza, S. Zambon, S. Giuliani, S. Romano, G. Tranchida, L. G. Bellucci, M. Vecchiato, F. D’Agostino, M. Frignani
Polycyclic Aromatic Hydrocarbons in samples from the southwestern Bac Giang Province and the Cau River (northern Vietnam)...................................................................................................... 91 S. Giuliani, R. Piazza, S. Zambon, M. Vecchiato, F. P. Polo, S. Romano, L. G. Bellucci, M. Frignani
Comparing italian and vietnamese legislations for the environment .. 103 S. Giuliani, S. Zambon, L. G. Bellucci, M. Frignani
Considerations on improving environmental monitoring in the Bac Giang Province and the Cau River (northern Vietnam) .......................111 S. Romano, S. Giuliani, L. G. Bellucci, M. Frignani
Annex 1. National Technical Standards of Vietnam.............................. 119 Annex 2. Comparison of quality standards and emission limits.......... 143
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Introductory note to the volume Riccardo Mattei Director of the Local Technical Unit – Italian Development Cooperation Embassy of Italy 9, Le Phung Hieu Street, Hanoi, Vietnam
I am pleased and honored to write an introductory note to this volume because I have followed closely the development of GVC’s project in the province of Bac Giang, from the time I moved to Vietnam, in 2012. The involvement and the results obtained by this NGO in the water and sanitation, environmental and agricultural sectors in the three districts of Hiep Hoa, Viet Yen e Yen Dung are astonishing, and the positive impact on people’s life is undeniable. GVC managed not only to deliver to the districts, with the support of the Department of Natural Resources and Environment-DoNRE and the Department of Agriculture and Rural Development-DARD, what it had planned (6 wastewater treatment plants, waste disposal and composting facilities, 150 biogas plants, etc…) but it built capacity within the communities, ensuring the sustainability of the initiative. In fact, its sustainability has also been granted by a high degree of involvement and integration among stakeholders: the inclusion of the Farmers Union and the creation of several Local Working Groups focused on the definition of needs of the community and on the most appropriate and effective response to them. This led to a substantial involvement in the agricultural sector, which made it possible to set up a robust organic-crop production hub that now supplies the markets of Hanoi, meeting the growing demand for organic produce. An important component of this initiative has been community based capacity building, which enables the project to “live even beyond its life”:
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the internalization of what has been learnt and taught will improve the life of the communities living in the districts, thus creating a better starting point for future initiatives and local development. An ex-post evaluation carried out by UCODEP (Oxfam Italia) and GVC has demonstrated that pollution has been reduced and quality of life of the local population has increased within the time of the project, which means that in all likelihood a radical change has begun to happen and the magnitude of the positive impact of the project will grow with time. For all these reasons I think that the initiative has proved to be very successful on a number of levels and I hope that the achievements obtained by the NGO in partnership with the communities can be replicated elsewhere, thus creating a model of good practice.
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Proceedings of the workshop “Environmental Quality in the Province of Bac Giang and the Cau River Basin. Perspectives for the improvement of monitoring activities and methods”. Hanoi, August 27th, 2013. Paper No. 1
Presentation of the Project “Promotion of environmental protection in the Viet Yen, Yen Dung and Hiep Hoa districts in the Bac Giang Province, Vietnam”: implementation, strategies and results Margherita Romanelli Desk Officer NGO Civil Volunteer Group (GVC) Via dell’Osservanza 35/2, 40136 Bologna, Italy
Tóm tắt – Trong khuôn khổ phiên thảo luận mới cho Chương trình nghị sự phát triển sau năm 2015 và các mục tiêu phát triển bền vững mới phù hợp với Hội nghị Rio + 20 một hợp tác mới giữa các tổ chức Phi chính phủ, các viện nghiên cứu, các tổ chức xã hội dân sự, các chính phủ và các tổ chức quốc tế cam kết trao đổi hỗ tương với các nước đang phát triển và các nước đang chuyển đổi, nơi Bắc và Nam phải chấp thuận một sự hợp tác mới, chặt chẽ hơn và phải tham gia thực sự trong việc quản lý tốt chung để đảm bảo sự phát triển xã hội, kinh tế và môi trường bền vững của cả hành tinh. Xuất phát từ cách nhìn nhận này, chương mục đề xuất thảo luận về kinh nghiệm thu được trong quá trình thực hiện dự án "Thúc đẩy bảo vệ môi trường ở các xã Việt Yên, Yên Dũng, huyện Hiệp Hòa, tỉnh Bắc Giang, Việt Nam", nhằm mục đích phục hồi và bảo tồn tài nguyên thiên nhiên và cải thiện điều kiện sống của người dân địa phương của tỉnh Bắc Giang, cải thiện việc quản lý các yếu tố gây ô nhiễm và tăng cường năng lực của các tổ chức địa phương để ngăn chặn thảm họa môi trường do con người gây nên và quản lý nguồn nước và tài nguyên sinh thái của khu vực đó. Các phương pháp tiếp cận đa chiều và đa mục tiêu là rất quan trọng để đạt được tham vọng là tránh và giải quyết suy thoái môi trường, và đề xuất một mô hình phát triển có tính khả thi và bền vững cho các quốc gia phải đối mặt với thách thức trong việc xóa đói giảm nghèo. Hợp tác quốc tế có thể đóng một vai trò quan trọng trong việc hỗ trợ mạng lưới trao đổi giữa các nước về mặt kỹ thuật cũng như chính sách. Trên giao diện này có thể kể đến sự hợp tác Hợp tác giữa CNR- ISMAR của thành phố Bologna và các đối tác cũng như hoạt động tăng cường bảo vệ môi trường thực hiện tại tỉnh Bắc Giang mà kết quả được giới thiệu trong tuyển tập này. Abstract – In the frame of the new debate on the Post-2015 Development Agenda and the new sustainable development goals consistent with the Rio+20 Conference a new partnership bringing together NGOs, research
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institutes, civil society organizations, governments and international institutions engaging themselves in a reciprocal exchange with developing and in transition countries, where North and South have to agree on a new and tighter cooperation and on a real participation in the common good management can ensure the sustainable social, economic and environmental development of the entire planet. Moving from this belief, the chapter proposes a discussion over the experience carried out within the implementation of the project “Promotion of environmental protection in the Viet Yen, Yen Dung and Hiep Hoa districts in the Bac Giang Province, Vietnam”, aimed at the restoration and preservation of the natural resources and improvement of life conditions of the local population of the Bac Giang Province, improving the management of the pollutant factors and increasing the capacity of local institutions to prevent environmental disasters originated by man-made hazards and to manage the water and ecological resources of that area. Multidimensional and multi-target approaches are crucial for the ambitious objective of avoiding and tackling environmental degradation, and proposing a feasible and sustainable model of development for those countries facing the challenge of poverty eradication. International cooperation can play a pivotal role in facilitating the networking for a mutual exchange encompassing technical and policies’ aspects. In this frame can be read the cooperation with CNR-ISMAR of Bologna and partners and the work to strengthen environmental protection carried out in the Bac Giang Province whose findings are presented in the present Volume.
The present work is the result of activities carried in the frame of a tight cooperation between Italian and Vietnamese actors to contribute to the promotion of a new sustainable development model where the protection of natural resources is a fundamental pillar for respecting the life in all its forms, where a renewed effort to affirm the leadership of human and environmental rights is the basis for a new pattern for global citizenship. NGOs, civil society, local and national authorities, research institutes and the private sector are all called to respond to this big challenge. With this aim GVC, CNR-ISMAR and their partners have started since 2010 a cooperation programme with the Province of Bac Giang, its main institutions and local CSOs to find together the best and feasible solutions where the environmental resources, for their nature of common goods, are preserved and restored towards an economic and social progress that respects rights also of those more vulnerable groups and future generations.
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Vietnam is situated in Southeast Asia, and as other countries in that region, is experiencing a period of deep economic transformation, from a planned to an open and market economy, with the renovation of the productive sector under a series of reforms started in the mid 1980, called Doi Moi, “renovation”. These reforms led to very high economic growth rates, higher than 9% per annum. GDP growth rates then slowly decreased, and today the data provided by the World Bank report an annual growth rate of 5.4% in 2013. The intense socio-economic development caused a significant increase in demographic growth as well, the population grew at sustained rates, reaching a peak of an annual 2.5%, and now rates are around an annual 1%. Great progress has been achieved by Vietnam in its effort to reaching the Millennium Development Goals, in particular the first goal concerning poverty reduction. In few years poverty 1 fell from nearly 60% in the early 1990s to 17% in 2008, and malnutrition 2 fell from 37% in 1993 to 12% in 2010, achieving the first UN Millennium Development Goal five years before than expected. Nevertheless, the development of Vietnam does not consistently involve the whole population, the pace of reduction is not equal among regions and, as it is often the case with fast growing economies, inequalities are rising and poverty rates among ethnic minorities and the most vulnerable members of society, as women, children, migrants or people living in disadvantaged areas, remain high. New forms of poverty are also emerging, in dimensions other than income, such as housing, water and sanitation, limited access to basic social services and social security. Vietnam is also registering an alarming increase in pollution levels, since the intensification of productive activities, industrial as well as agricultural, was not sustained by an adequate management of natural resources. A stronger effort is thus necessary in order to reach the targets set up by Millennium Development Goal number 7, that related to
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Poverty headcount, % (Data provided by the World Bank, as of September 2014) Prevalence (%) of malnutrition, weight for age of children under 5 (Data provided by the World Bank, as of September 2014) 2
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environmental sustainability and including other topics such as biodiversity conservation, climate change or improved sanitation and hygiene. Reaching internationally set-up economic indicators has proven not to be sufficient in order to improve the life standards of the local population. Vietnam, without a sustainable and equal development, will not be able to keep the growth rates high, nor to face the pressure of an increasing population, and it will be more vulnerable in front of the disastrous climate changes and events that currently, especially in Southeast Asia, are happening more and more frequently and intensely. Vietnam needs to find a new, sustainable and equal path towards development that, in order to ensure a long-term growth, has to take the needs of all population groups and the limits of our planet’s natural resources – adopting environmental mitigation and compensation measures - into consideration. The improvement of the general wellbeing of the population cannot be ensured by the sole economic growth, but it is necessary to implement measures capable of addressing to the social, economic and environmental sustainability as well, pursuing the human – and not just the economic – development of the entire country. When looking at the UN Human Development Index, Vietnam is just 121st out of 187 countries, because of the persistent problems that remain unsolved, as the exclusion of the population living in the most disadvantaged areas from the development processes, which are not sufficiently fair and sustainable, and as the need for more efficient measures to protect the natural and environmental resources. Civil Volunteer Group, GVC, works in Vietnam since the early 1990s in the Bac Giang and Thua Thien Hué provinces. At the beginning, GVC
developed
mostly sanitation,
education,
food
security and
development projects, financed by the Italian Ministry of Foreign Affairs, by Italian public authorities and by European funds. In the most recent years, GVC’s activities adapted to the changing context and addressed to the emerging problems of the Vietnamese women and men in need. New
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projects have been promoted for the inclusion of the most vulnerable population and for the protection of natural resources, thanks to sustainable measures. GVC paid great attention on the situation of the inhabitants of the Bac Giang Province, an area in the North of Vietnam, just 60 km far from Hanoi, and today one of the most affected by the consequences of an accelerated and not completely controlled industrial development, boosted by foreign investments. The Bac Giang Province lays in the area of the Cau river basin, one of the most polluted rivers in the whole Vietnam. The recent rapid growth of the population in that area, along with the proliferation of new industrial and agricultural activities, caused a significant increase in the quantity of waste, both organic and inorganic, produced and then poured in the surrounding environment. The lack of an appropriate integrated system for the collection and disposal of the waste produced, and the lack of awareness and consciousness among the population regarding the importance of protecting the environment, worsened the ecological degradation and the pollution of that area, leading to devastating effects for the natural resources, like soil and water, endangering the long-term perspective for the economic development and, most importantly, damaging the citizens’ quality of life. From a regulatory point of view, Vietnam adopted a quite advanced environmental protection legislation, yet it is still difficult for local authorities to implement it at a peripheral level. Local authorities and local environmental protection departments need therefore greater support, both in terms of training and techniques, to meet national standards and to respect the current regulations. The Vietnamese government itself chose to include the Bac Giang Province among the priorities areas for its environmental rehabilitation strategy. In this context, in 2010 GVC, in collaboration with UCODEP/Oxfam Italia, the experts from the Italian Institute of Marine Sciences (ISMAR) of the National Council of Research (CNR) in Bologna, the department of Environment and Natural Resources (DoNRE), the department of
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Agriculture and Rural Development (DARD) of the Bac Giang Province, supported and implemented the project “Promotion of environmental protection in the Viet Yen, Yen Dung and Hiep Hoa districts in the Bac Giang Province, Vietnam”, lasting three years and financed by the Italian Ministry of Foreign Affairs and International Cooperation (MAECI) and two Italian local authorities as Provincia Autonoma di Bolzano and the Friuli-Venezia-Giulia Region. The project aimed at the restoration and preservation of the natural resources and improvement of life conditions of the local population of the Bac Giang Province, improving the management of the pollutant factors and increasing the capacity of local institutions to prevent environmental disasters originated by man-made hazards and to manage the water and ecological resources of that area. All actions developed within the project were ultimately aimed to contributing to poverty reduction and to increasing the soil productivity pursuing a sustainable approach in the Bac Giang Province, in the districts of Hiep Hoa, Viet Yen and Yen Dung, in the municipalities of Thang Coung, Tu Mai, Yen Lu, Van Ha and Hoang Ninh. Environment degradation is in fact among the emerging most relevant causes of insufficient agricultural production, both in terms of quantity and quality. The methodology adopted by GVC moves from the belief that a multidimensional approach is necessary to tackle effectively those factors affecting the interlinked pair of natural resource degradation and poverty. Being out for development cooperation only to solve those big challenges the country faces, within the project a range of different actions could be put in place to exchange mutual valued experience and good practices matured both in Vietnam and Italy in a profitable dialogue and practices to find together feasible and adequate solutions to address environment and development issues. Based on the object to protecting and affirming the basic rights to food, water, health for present and future generations, the project has proposed an integrated action involving agriculture production, water management, waste treatment and pollution monitoring.
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Three main tracks were followed by the intervention. They were modelled considering the results of an initial baseline assessment conduced among households in the target area. Firstly, the project proposed specific practices to reduce the impact of pollution and environmental degradation and preserve natural resources to be used in a sustainable manner. Specifically it responded to the request for clean water for domestic use, waste management solutions, more sustainable agriculture. In this frame GVC and partners acted to: - Ensure access to basic natural resources to the growing population. In particular in response to the need of clean water for domestic use, three water treatment plants were built in Van Ha and Thang Coung, now providing clean water for 10,300 people. The project also supported local municipalities, owner of the plants, to arrange an efficient and effective management of the service. Considering the low skills of local public technicians and the availability of local private enterprises with sufficient experience, skills, water and energy, municipalities decided after a long and detailed negotiation to arrange an agreement to put the company in charge of the plant management. GVC experts provided technical assistance to the local authorities to find an agreement with that company to ensure the best quality and the largest access to the service safeguarding the public utility and common good nature of water. - The almost total lack of a waste management system not only was perceived by the local authorities as a problem, but also citizens have expressed the need to find a solution to the issue. However, a complete awareness of all and interconnected consequences in terms of health, and quality of natural resources as water and soil were not yet fully understood by the population. Beside, household’s daily practices strongly affected environment as well as the high use of chemical input in agriculture. In the framework of the project, two compost containing plants were also built, for the sustainable disposal of organic domestic and urban waste in the municipality of
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Van Ha, serving 8,670 people and producing 900 tons of compost per year from agricultural waste, used as organic fertilizer instead of the chemical fertilizers massively used by local farmers before. Plants allow also 400 tCO2/equivalent reduction of missions each year. In order to ensure an adequate urban waste collection and appropriate safety working conditions, 500 protective systems for collectors, 300 containers for waste management in schools and sanitary centres and 50 serving carts for waste transportation were distributed. Moreover 150 biogas plants were installed for the domestic use of families, ensuring a sustainable access to energetic resources, protecting the environment and reducing waste: the installation of biogas plants allows the production of natural gas treating the organic waste domestically produced and the reduction of CO2 equivalent missions by 675 tons per year. - The production of biological rice and vegetables and the related reduction in the use of chemical fertilizers and insecticides in 5,000 hectares of paddy fields and 500 hectares of orchards and crop fields. The successful implementation of these activities was possible thanks to the collaboration with public authorities and universities, that organized theoretical and practical courses about the use and marketing of natural and biological techniques and products for local technicians, administrators and for 515 families of smallholder farmers.
Secondly, acknowledging development as a process of participation where change is the fruit of dialogue and composition of interests and potentiality of different groups/stakeholders into the community, within the project tools were used and leverages were activated to increase democratization in terms of planning and monitoring of natural resources practices of preservation and restoration. Addressed to the population,
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information and awareness campaigns on the need to adopt eco-friendly behaviour and culture were carried out to involve schools and hospital; addressed to authorities, information, visibility and advocacy activities were implemented to promote dissemination, replication and possibly scaling up of the activities. For this aim GVC and its partners: - Created Five Local Working Groups (LWGs), composed by the representatives of the villages, municipalities, and of the Union of Women, in order to involve the local population in the designing and in the implementation process of activities and in the management of environmental resources. The 15 micro-interventions developed with the LWGs were aimed to the preservation and restoration of the natural resources of the beneficiary area, though, for example, the construction of small landfills, reforestation interventions, biological production or the construction of a temporary warehousing site for a sanitary centre. - Used training as a pivotal tool of capacity building addressed to local staff, in order to strengthen their technical expertise as well as to ensure the inclusive management of the project. Training has concerned organic and inorganic waste management and treatment techniques, selective waste collection and management of pollutant factors in water and soil and inclusive planning, monitoring and assessment. Local administrators, members of LWGs and of local associations of women and farmers, environmental monitoring technicians, waste collectors, school and hospital staff members participated in these meetings, courses and training sessions. These achievements were possible thanks to the collaboration with a number of Italian and Vietnamese high qualified experts. The work on the field highlighted the will of Vietnamese of receiving advices and sharing practical experiences. In the spirit of this reciprocal exchange, 6 training scholarships have been also provided for Vietnamese technicians to participate in training and meetings with Italian institutions. The courses took
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place at the CNR-ISMAR UOS centre in Capo Granitola, Sicily, Italy, and at the Department of Environmental Sciences, Informatics and Statistics of the Università Ca’ Foscari of Venice for theoretical and practical training. Exchange of knowledge was also managed through organization of meetings between Italian/Vietnamese institutions and technicians and during a study visit to important Italian experiences in the field of compost and water treatment (CNR of Bologna and Venice, at the municipalized company for clean water of Reggio Emilia, the Committee for Public Water of Bologna, the cooperative Nuova GEOVIS for waste management and composting of Reggio Emilia, the Consorzio Italiano Compostori, the Italian Association for the production of compost and biogas and the CoopNordest cooperative for in the field of agro-food industry and sustainability). - The project also included promotion activities, consisting of three information campaigns about the proper management of waste, recycling and selective collection disseminated trough local media (articles and drawings in local newspapers, dedicated programs broadcasted on TV and radio) and of communication campaigns in 10 schools, 5 hospitals and public offices in the beneficiary districts and municipalities about the preservation of natural resources and the proper management of organic and inorganic waste.
Thirdly, the project enhanced the implementation of an institutional frame for monitoring the status of the environment. As said, despite Vietnam has a quite boosted legislation at national level, its implementation in terms of local regulation, roles of agencies in charge of and capacity of their staff shows strong constraints. Therefore, the project facilitated the collaboration of Italian high level qualified actors and Vietnamese subjects playing a pivotal role in establishing rules, procedures and control over the natural resources protection. The collaboration with CNR – ISMAR of Bologna together with Ca’ Foscari University of Venice gave an important
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added-value to the project, introducing precious elements for innovation. CNR’s experts together with CEM staff carried out a detailed analysis of pollution factors in the Cau river area encompassed in Bac Giang province, whose results are reported in the following chapters of the present publication. Moving from those results, a larger analysis over legal Vietnamese framework and institution on environmental issues have been carried out to promote a more efficient environmental monitoring systems and to provide the local authorities with the necessary instruments to properly manage them. Findings and recommendations were critically discussed in some workshops participated by the main Vietnamese actors working with the environmental protection. The improvement of the environmental monitoring system in the Province of Bac Giang was not important just from a scientific point of view, but it also allowed discussions about the Vietnamese environmental regulatory framework, advanced in theory but difficult to implement in the peripheries. This debate also stimulated a more inclusive and democratic participation of civil society in the mechanisms of active citizenship, engaging them in discussions with local policy-makers and administrators about the inputs to introduce in the environmental monitoring systems to allow an adequate implementation of the national regulation in the local districts and municipalities. This information and feedback sharing among different levels of governance contributed to the improvement of the capacity of local authorities to adapt to the national standards and raise awareness about the need to protect the environment in the whole country. Activities carried out were able to outreach 41,000 inhabitants of the highly polluted districts of Hiep Hoa, Viet Yen and Yen Dung in the Bac Giang Province, targeted by information and communication campaigns on environmental and sustainable agricultural topics. 10,300 inhabitants could directly have access to the clean water thanks to the construction of the water treatments plants and 9,426 could benefit from the waste treatment systems and from micro-interventions. Moreover, 1,840 members of the technical local staff of districts, municipalities, schools, sanitary centers,
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associations, waste collectors, companies and fertilizers’ traders participated in courses, training sessions, conferences and visits to Italy and 515 smallholder families were introduced to biological agriculture. Some events arranged within the project included seminars about the environmental monitoring system, involved several representatives of national Ministries, local Departments, Districts, Municipalities and the civil society. The aim and results of the project could then be illustrated to the Vietnamese authorities, enhancing the possibilities for its dissemination and replication in other areas of the country. The implementation area of the project also became the destination of institutional visits, in particular from representatives of other Provinces, even far from Bac Giang, that could adopt the same measures. Speaking more deeply about the impact of the project, it was measured through a comparative/longitudinal (2010-13) analysis between information collected among the resident population in the target area where extensive quality as well as quantity information on environment and local population has been collected. The survey was structured on the basis of a multiple choice test, form which three indicators have been developed: IEKC - indicator of environmental knowledge and consciousness, ISBN indicator of satisfaction of the basic needs and IFR - indicator for family recycling. The first data collection occurred at the beginning of the project, during 2010. In 2013, when all the activities of the projects were concluded, the population was tested on the same questionnaire, in order to compare data and assess the impact of the activities of the project and provide useful suggestions to local stakeholders on how to follow up or scale up activities carried out in the target areas. The results showed that after the project environmental knowledge and consciousness increased (IEKC), meaning that the population had a deeper understanding and awareness about the environment. Indicator for family recycling (IRF) also increased proving the change of habits for families in waste management. On the contrary, the indicator of satisfaction of the basic needs decreased (IFR), but mainly because of the sub-indicators related to sanitary systems, primary and
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secondary education, public transportation and land for agricultural use, topics that anyway did not relate to the objectives and sectors of intervention of the project. Reading through the achieved results it is possible to highlight once more that it was out of the scope of the project to provide a response to the multiple and complex basic needs of the population that in turn are effected by a lot of different elements. For this reason they can only be the ultimate objective of the Vietnamese Government policies. However, thanks to the project a range of good and innovative practices have been realized with positive outcomes. Such experiences can represent good basis to address and support with knowledge sharing the Governmental action in scaling up those positive results achieved by the project. Moreover, the analysis shows the project was able to push a change in the cultural approach of local population towards a better relationship with the environment. It has been paved the way to a spread adoption of a new individual and households’ behaviour and habits increasing the natural resource protection. The achieved results were possible thanks to a participative methodology applied and oriented towards the collaboration between GVC, the Italian partners and the local associations, institutions and local population. A real network was activated, involving Italian and Vietnamese subjects, for a significant exchange of technical, environmental and social expertise; policy-makers, representatives of local authorities and civil society worked together to face a problem difficult to solve, as sustainable development, related to many topics such as access to water, sustainable agriculture, waste management and environmental monitoring. Real change is achievable by improving synergies between civil society, the population’s needs and endogenous human and social resources, political will, financial and physical capital, technical and communication capabilities. Thus, it is crucial that NGOs, research institutes, civil society organizations, governments and international institutions engage themselves in a reciprocal exchange with developing countries, and countries as Vietnam, that progressed in the reduction of poverty goals, but that have still
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to face the consequences of an uneven development, not sustainable in the long period. This suggests two orders of considerations. Firstly, building a boosted partnership implies medium-long term perspective. Too many times international cooperation mechanism is subjected to the need to be accountable in a short time framework about the results achieved, missing then to provide sustain and funds to interventions for and adequate time span enabling the consolidation of relationships and a real impact evaluation of the activities carried out. Secondly, more recent development strategies of major donors as the European Union or the Italian Minister Of Foreign Affairs and International Cooperation are addressed to the last income developing countries. Even this choice to concentrate resources towards more in need countries can be understandable, but it should not be underestimated the inequalities and the environmental challenges middle income development countries face. In their delicate phase of acceleration towards development, adoption of models neglecting natural resources protection and those more vulnerable people (are them the most affected by the environmental degradation), are the basis for a future and global unsustainability. Therefore, particular attention should be paid by the international community as a whole to the promotion of new paths for progress and wellness to be adopted by emerging countries and to be used to progressively adjust those of developed ones. More organic and coherent polices and instruments of cooperation should be adopted, building upon results achieved in the first stages of development, enhancing the participation of those partners that have contributed to, beside the entrance of new ones. Among them a new role of the private sector is acknowledged being relevant when adopting a real social and environmental responsible behaviour. In our current globalised world, more and more interconnected, North and South countries have to agree on a new and tighter relation to ensure the sustainable social, economic and environmental development of the entire planet, in the framework of a new partnership really global and
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committed, pursuing the new sustainable development goals consistently with the Rio+20 Conference and the debate on the new development frame that are going to be set up in the Post-2015 agenda.
Acknowledgements The author wish to thank G. Santavicca, and his assistants Dario Cesarini and Antonietta Intini and all GVC local staff, for managing the GVC-UCODEP project “Promotion of Environmental Quality in the Districts of Viet Yen, Yen Dung and Hiep Hoa in the Bac Giang Province, Vietnam“ and Ms. Huong Le Thi Bich having voluntary contributed to the Vietnamese translation of the present work. Moreover a strong thank to M. Frignani, S. Giuliani, S. Romano, L. G. Bellucci, S. Zambon, C. Turetta, M. Vecchiato, R. Piazza, G. Tranchida, F. D’Agostino, C. Barbante, F. P. Polo, of CNR and the University of Venice for the scientific contribution to the project activities especially in terms of PCBs, PBDEs, PCDD/Fs, chlorinated pesticides and hydrocarbons in soil and sediments sample collection and analysis as well as environmental monitoring plan recommendations. Furthermore, the author thanks Vietnamese partners for a tight and profit cooperation: the Bac Giang Province and especially the Department of Natural Resources and Environment, Yen Dung, Viet Yen and Hiep Hoa districts, Thang Cuong, Tu Mai, Yen Lu, Van Ha and Hoang Ninh communes; Centre for Environmental Monitoring, Vietnam Environment Administration. Finally, a special thank to the Italian Minister of Foreign Affairs and International Cooperation, DGCS and especially to Riccardo Mattei of Hanoi UTL, Autonomous Bolzen Province and Friuli Venezia Giulia Region because without their financial contribution and support the project could not have ever been implemented.
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Proceedings of the workshop “Environmental Quality in the Province of Bac Giang and the Cau River Basin. Perspectives for the improvement of monitoring activities and methods”. Hanoi, August 27th, 2013. Paper No. 2
Water Quality Trends of the Cau River Basin from 2008 to 2012 Nguyen Van Thuy, Nguyen Huu Thang, Nguyen Duc Thanh, Nguyen Hong Hanh Centre for Environmental Monitoring, Vietnam Environment Administration No.556 Nguyen Van Cu Street, Hanoi, Vietnam
Tóm tắt – Trong bài này, chất lượng môi trường trên các nhánh sông chính của lưu vực sông Cầu được đánh giá qua giai đoạn 5 năm (2008 – 2012). Các thông tin dữ liệu (DO, COD, BOD5, TSS, Coliform, sắt, amôni, nitrit và nitrat) thường vượt ngưỡng cho phép theo quy chuẩn đánh giá chất lượng nước QCVN08:2008. Dựa vào các kết quả quan trắc, chất lượng nước sông Cầu có xu hướng giảm về hạ nguồn, đặc biệt khi qua Thái Nguyên và hai tỉnh Bắc Giang và Bắc Ninh. Ngoài các điểm ở hạ nguồn bị ô nhiễm, một số điểm ở thượng nguồn qua Bắc Kạn cũng đã có dấu hiệu suy giảm chất lượng môi trường. Điều này đòi hỏi cần đẩy mạnh công tác quan trắc và thanh tra tổng thể toàn lưu vực sông Cầu nhằm đưa ra các giải pháp kịp thời. Abstract – In this article, the water quality trend of the main tributaries of Cau River is described over a five year period (2008-2012). The data (DO, COD, BOD5, TSS, Coliforms, Fe, ammonia, nitrites and nitrates) often exceeded the permitted threshold of the Vietnam National standard for surface water quality QCVN 08:2008. The water quality at Cau River tends to decrease downstream, especially when entering Thai Nguyen and the two provinces of Bac Giang and Bac Ninh. Moreover, not only downstream locations, but also the upper part of Bac Kan showed a decreasing water quality in recent years. The results suggest the need of an improved monitoring activity together with inspections and studies to devise appropriate management solutions. Keywords: water quality, monitoring, Cau river basin, physico-chemical parameters
1. Introduction The Cau River is the main tributary of the Thai Binh River and its basin accounts for as much as 47% of the overall territory. Due to the fast economic and social development of the area, the environmental problems
19
have become more and more complex over time. In 2005, the Vietnam Environment Administration in collaboration with a number of other organizations developed the Master Plan for a water quality monitoring programme for the Cau River basin. The activities, based on water sampling and analysis several times a year, generated a continuous data set from 2006 till now. This article will present status and trends of water quality of Cau River and its main tributaries over the period 2008-2012. The river water quality is expressed through some main physico-chemical and biological parameters including Dissolved Oxygen (DO), Chemical Oxygen Demand (COD), Biochemical Oxygen Demand (BOD5), Total Suspended Solids (TSS), Coliforms, Iron (Fe), Ammonium (N-NH4+), nitrite (N-NO2-) and nitrate (N-NO3-).
2. Materials and methods 2.1. Study area The Cau River (Fig. 1) originates from the Tam Dao mountain (elevation of 1,326 m), passes though the Cho Don commune (Bac Kan province) and the provinces of Thai Nguyen, Bac Ninh, Bac Giang and ends in the Red River at Pha Lai, Chi Linh, Hai Duong. The river is 288 km long but the overall catchment length is 1,600 km. The river basin is characterized by a high population density, with 648 inhabitants per square km, which is approximately 2.5 times higher than the national average. In recent years, the river basin has been seriously impacted by intensive industrial and mining activities, particularly in sand and gravel exploitation sectors.
2.2. Monitoring The state of water quality in the main stretches of Cau river basin is here described, including the monitoring results for the 16 sampling locations that were sampled continuously in the period 2008-2012. The representations in Figs. 2-9 follow a substantially geographic order (from the upstream site at Cau Pha to the downstream station at Yen Dung).
20
Figure 1: Map of the Cau river basin.
Field sampling and lab analyses were made at the Centre for Environmental Monitoring (CEM) following the methods described by the Circular No. 29/2011/TT-BTNMT, issued in August 2011, on “Technical regulation for inland surface water quality monitoring”. QA/QC was applied during the entire process to ensure the reliability of obtained data. These
21
procedures were then the object of the Circular No. 21/2012/TT-BTNMT issued in December 2012 on “Regulation on the quality assessment and quality control in environmental monitoring”. Specifically:
Sampling method: The methods for collecting samples, their processing and storage were in accordance with the ISO regulations on monitoring surface water quality.
On-field measurements: pH, temperature, electrical conductivity (EC), total dissolved solids (TDS), and DO were measured on the field using the fast measurement equipment Horiba U22XD. Measurements were taken by dipping the electrode directly into the water sample, and reading the results after the attainment of proper conditions.
Sample treatments in the laboratory: Laboratory methods are listed in Table 1. Most of them are in accordance with SMEWW (Standard Methods for the Examination of Water and Wastewater), whereas nitrates were measured using the Vietnam Standard, TCVN 6180:1996).
Table 1: List of laboratory analytical methods No.
Parameter
Analysis method
1
COD
SMEWW 5220C
2
BOD5
SMEWW 5210.B
3
Nitrites (N-NO2-)
SMEWW 4500.NO2-.B
4
Nitrates (N-NO3-)
TCVN 6180:1996
5
Ammonia (N-NH4+) SMEWW 4500 - NH3- F
6
TSS
SMEWW 2540D
7
Fe
SMEWW 3500 – Fe
8
Coliforms
SMEWW 9222 B
22
Equipment calibrations: All equipments were calibrated when necessary following the standard guidelines. Furthermore, after one year in operation equipments were sent to the Standards, Metrology and Quality Administration department - Vietnam Metrology Institute for Calibration.
QC controls: Each day, following the quality control regulation, the laboratory processed some basic samples before analyzing field samples, including: 1) blank samples; 2) GGA sample (concentration approx. 300 mg/l); 3) duplicate samples (5 to 7 % of the total) and 4) CRM samples. All laboratory procedures were recorded in a diary and periodically reported. Each year, samples for the international quality checking activities were exchanged with other standard laboratories in the Asian region as well as Inter. Cooperation Agencies such as JICA (Japan) and KOICA (Korea).
2.3. Data analysis and reporting All the data were stored in a database of the Vietnam Environment Administration and used for all further elaborations. Results were compared with the National Technical Standards for surface water quality QCVN 08:2008/BTNMT: 1) type A2, that can be used for water supply purposes after an appropriate treatment technology, and for conservation of aquatic plants; 2) types B1 and B2 that can be used for irrigation or others similar uses. The details of the standard QCVN 08:2008/BTNMT are provided in the Annex to this volume.
3. Results and discussion 3.1. Water quality status on main tributaries of Cau river basin in the period from 2008 to 2012 Dissolved Oxygen (DO) DO values showed a decreasing trend from upstream (point Cau Pha, Bac Kan province) to downstream (Yen Dung commune at the interception
23
between Bac Giang and Bac Ninh province). Only once, in 2008, four values of DO were measured at downstream locations that did not satisfy the standard QCVN 08:2008 type A2. In general, DO values remained stable and uniform over time and space.
Figure 2: DO trend at Cau River from 2008 to 2012.
Chemical Oxygen Demand (COD) According to the monitoring data collected from 2008 to 2012, COD slightly increased at Thai Nguyen and substantially peaked up in Bac Ninh and Bac Giang provinces. Specifically, the annual average value was very high in 2012 with the utmost monitoring data around 28 mg/L at at Hoa Long sampling site (Bac Ninh province). However, none of the results exceeded the QCVN 08:2008 type B1. High values of COD in correspondence of both Bac Ninh and Bac Giang provinces were explained due to the direct wastewater discharge (without any pre-treatment) from nearby households and craft villages. The effects were possibly enhanced by the rapid development of industries and urbanization in the region.
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Figure 3: COD trend at Cau river basin from 2008 to 2012.
Biochemical Oxygen Demand (BOD5) Similarly to COD, BOD5 also showed marginal elevation in Thai Nguyen and reached a higher pollution level at sites influenced by the two provinces of Bac Ninh and Bac Giang. The water quality decreased more in 2011 and 2012.
Figure 4: BOD5 trend at Cau river basin from 2008 to 2012. Total Suspended Solids (TSS) TSS values fluctuated in a complicated way over time and space. In 2011, a result was unexpectedly high at the upstream point at Bac Kan, although it was low over the rest of the time, just below the technical standard of QCVN 08:2008 type A2.
25
Figure 5: TSS trend at Cau river basin from 2008 to 2012.
Nitrogen containing compounds Ammonium showed a gradual increase downstream, from the Thai Nguyen province to Bac Ninh and Bac Giang. However, the data in 2010 did not follow such a trend, with the significantly high data upstream after Bac Kan, especially at Van Lang. and. The QCVN 08:2008 type B1 was exceeded.
Figure 6: N-NH4 trend at Cau river basin from 2008 to 2012. Nitrite concentrations tend to increase at Thai Nguyen and remain high in correspondence of the two downstream province of Bac Ninh and Bac Giang. Most of the annual average value did not meet the standard QCVN 08:2008 type B1. In 2010 high value were found even upstream (especially at Cau Pha) in Bac Kan province.
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Figure 7: N-NO2 trend at Cau river basin from 2008 to 2012. Coliform The mean value over years of Coliform content did not increase downstream but remained complicated, with no clear patterns. In 2010, the results were extremely high, exceeding the standard QCVN 08:2008 type B1 many times.
Figure 8: Coliform trend at Cau river basin from 2008 to 2012.
Major and trace metals Trace metal (such as Pb, Hg, Cu, Zn...) concentrations along the Cau River in the study period satisfied the requirement of the QCVN 08:2008. Among major elements, Fe was the sole exceeding the permitted threshold.
27
The increasing trend of Fe was similar to those of many other parameters, with higher levels moving downstream. The highest value of Fe was found in 2009.
Figure 9: Fe trend at Cau river basin from 2008 to 2012.
3.2. Percentage of results exceeding the National standard QCVN 08:2008 from 2008 to 2012. According to the data summarized in Figs. 10 and 11 :i) DO results indicate a good water quality in recent years with the percentage of values that exceeded QCVN 08:2008 decreasing gradually over time; ii) the organic matter contents (as COD and BOD5) slightly exceeded the permitted threshold of QCVN 08:2008. However, COD tends to increase in recent years and, especially in 2012, 32.3 % of COD values exceeded QCVN 08:2008 type A2. This was also the highest rate of standard exceedence over the five year period; iii) nutrients (such as ammonium and nitrite) remained high, with a significant number of values exceeding the type A2 limit. Especially in 2008, the observations beyond the QCVN 08:2008 were 83.3 and 57.3 % for ammonium and nitrites, respectively; iv) coliform data remained complex over the years with no clear patterns. However, the percentage of values that exceeded QCVN 08:2008 was also quite large, from 26 % to 71.9 % with respect to the type A2 standard.
28
Figure 10: Percent of data exceeding the QCVN 08:2008 type A2 on the main streams of Cau River in period from 2008 till 2012.
Figure 11: Percent of data exceeding the QCVN 08:2008 type B1 on the main streams of Cau River in period from 2008 till 2012 4. Conclusions Along with the rapid social economic development, a number of environmental issues have become important, putting pressures on river basins in general and on that of Cau River in particular. This latter is influenced by a wide variety of waste sources from industrial and agricultural activities, mining, craft villages, towns and cities.
29
The contamination of the Cau River system tends to increase downstream, especially after Thai Nguyen and further passing the two provinces of Bac Ninh and Bac Giang. Changes in water quality are very complex. Distinct from the general trend of previous years, the results relative to the upstream parts of the river recently showed a significant improvement, especially regarding nutrients (ammonium and nitrite), total suspended solids and coliforms. The changes in water quality along Cau river basin over the five year period from 2008 to 2012, clearly suggest the need of appropriate strategies in water management all over the basin. These will have to include both an improvement of the monitoring design (e.g., by extending the number of parameters under control) and include some research to enhance the comprehension of the environment and the links with socioeconomic issues.
Acknowledgements The authors wish to thank M. Romanelli and G. Santavicca for managing the GVC-UCODEP project “Promotion of Environmental Quality in the Districts of Viet Yen, Yen Dung and Hiep Hoa in the Bac Giang Province, Vietnam“, funded by the Italian Ministry of Foreign Affairs, General Direction for Development Cooperation (DGCS). The authors are also indebted with M. Frignani and S. Giuliani for critical reading and suggestions.
References CEM, 2008. Monitoring results of water quality at Cau river basin in 2008. Overall program on environmental monitoring of Cau river basin. Synthetic report. Hanoi, Vietnam, pp. 140. CEM, 2009. Monitoring results of water quality at Cau river basin in 2009. Overall program on environmental monitoring of Cau river basin. Synthetic report. Hanoi, Vietnam, pp. 129.
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CEM, 2010. Monitoring results of water quality at Cau river basin in 2010. Overall program on environmental monitoring of Cau river basin. Synthetic report. Hanoi, Vietnam, pp. 131. CEM, 2011. Monitoring results of water quality at Cau river basin in 2011. Overall program on environmental monitoring of Cau river basin. Synthetic report. Hanoi, Vietnam, pp. 131. CEM, 2012. Monitoring results of water quality at Cau river basin in 2012. Overall program on environmental monitoring of Cau river basin. Synthetic report. Hanoi, Vietnam, pp. 131. SOE, 2006. Vietnam National Environmental report 2006 - State of water environment in three river basins of Cau, Nhue – Day and Dong Nai river system. Vietnam Environmental Protection Agency. Hanoi, Vietnam, pp. 92.
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Proceedings of the workshop “Environmental Quality in the Province of Bac Giang and the Cau River Basin. Perspectives for the improvement of monitoring activities and methods”. Hanoi, August 27th, 2013. Paper No. 3
Promotion of Environmental Quality in the Districts of Viet Yen, Yen Dung and Hiep Hoa in the Bac Giang Province, Vietnam: sediment and soil samples for environmental quality assessment Stefania Romano, Silvia Giuliani, Luca Giorgio Bellucci, Mauro Frignani CNR-Institute of Marine Sciences, Via Gobetti 101, 40129, Bologna, Italy
[email protected];
[email protected];
[email protected];
[email protected]
Tóm tắt – Để có được thông tin về chất lượng tổng thể của môi trường ở phía tây nam tỉnh Bắc Giang (miền Bắc Việt Nam) một loạt các mẫu được thu thập từ các con sông (sông Cầu, Ngũ huyện Khê), cánh đồng lúa, ao, vũng nước và giếng gia đình. Mẫu được phân loại theo kích thước hạt và các chất hữu cơ (carbon hữu cơ, nitơ tổng số, δ13C) trong thành phần trước khi phân tích các chất gây ô nhiễm chính. Abstract – To obtain information on the overall quality of the environment in the southwestern Bac Giang Province (northern Vietnam) a series of samples was collected from rivers (Cau, Ngu Huyen Khe), rice fields, ponds, puddles and family wells. Samples were characterized by their grain size, and organic matter (organic carbon, total nitrogen, δ13C) content. Samples were then analysed for major contaminants. Keywords: Soils and sediments, grain size, organic matter, Vietnam.
137
Cs, Bac Giang Province,
1. Introduction Contaminants enter the river system through various pathways. Hydrological conditions determine the contribution of the various sources and whether contaminated sediments remain in the riverbed or become more widely distributed over floodplains and wetlands. Contaminants in sediment may impact the ecological or chemical water quality status.
33
A common distinction is between point and diffuse sources of contamination; which reflects their behavior under changing meteorological conditions (Vink and Berendt, 2001). However, both of them contribute to the total contaminant load of rivers. Riverine material is characterized by a continuum of sizes from coarser grain to purely dissolved forms. ‘Dissolved compounds’ are transferred across aquatic systems together with the water, while the ‘particulate compounds’ are transferred differently: they may settle and be remobilized, according to flow velocity, particle size and shape, river bed morphology, etc. The fine and medium-sized particles, i.e. below 63 microns, are the most important. The properties of these fine particles (e.g. large specific surface areas, high ion exchange capacities) enable them to act as efficient scavengers of contaminants discharged into the river system. Moreover, when total suspended solids concentrations (TSS) exceed 100 mg/L, more than 90% of the most toxic metals, and major Persistent Organic Pollutants (POPs), are present in river, adherent to particulates (SedNet Strategy paper, 2004). The main goal of this study is to present the physico-chemical characteristics of samples collected for the study of environmental quality in the southwestern Bac Giang Province through their location and basic characteristics, such as grain size composition and organic matter content. Also the concentration of the radionuclide 137Cs was measured.
2. Study area The Bac Giang Province (first formalized in 1997) is located in Northern Vietnam and lies in the Red River Delta Region (Fig. 1). The weather regime has the dominant characteristics of the tropical, temperate climate zone of the Northern Plain. Temperature, humidity and rainfall vary over months and seasons. Since the province is located away from Vietnam's eastern coast and the South China Sea (East Sea), the incidence of hurricanes and storms is rare, with only localized phenomenon in few mountainous districts.
34
(b) (a)
Figure 1: Location of the Bac Giang Province (a) and its Administrative Map (b).
35
The Province borders Quảng Ninh to the east, Lạng Sơn to the north, Thái Nguyên and the urban district of Sóc Sơn in the capital Hanoi to the west, and Bắc Ninh and Hải Dương to the south (Fig. 1). It comprises three land forms, namely: the lowland or delta land, the midland and the mountainous region (Statoids, 2010). The Province economy is primarily dedicated to agriculture (31% of total land use). In particular, the Province is known as a producer of rice, vegetables, fruit crops and bulb trees. 27.7% of Bac Giang's area is devoted to forestry that produces wood and trees of bamboo and neohouzeaua. Different villages in the area are dedicated to wood handcrafts. The rest of the Province land is residential and urban. Moreover, the Bac Giang territory hosts mineral activity that involves the mining extraction of 15 types of minerals such as coal, metal, industrial minerals, building materials registered on the territory (Bac Giang Industrial Zones Authority, 2010). During the period 1997-2008, the province has launched several industrial projects in all its districts. As a result, several economic farming models were introduced, which resulted in "Rural Economic Development" amd social consumer retail sales. Services got a boost, the poverty rate (2005 level) reduced to 17.78%, and textiles and garment exports reached 76% of the province's export turnover (Bac Giang Department of Industry and Trade 2010). Infrastructures such as the National Highway, and rural roads were expanded. Key industries like fertilizer, high technology, engineering, building materials, assembling automobiles, agricultural processing, forestry products, textiles and electric power generation are planned with the objective of achieving a GDP growth rate of 11-12% by 2020 (Population and Employment: General Statistics Office of the Government of Vietnam, 2010). Navigation was part of its beneficial uses as a transport route for shipment of rice and salt from Hai Phong to Thái Nguyên. The scheme, as built, has a concrete across the Cau River, the mainstream of the Thai Binh River system (Bac Giang Department of Agriculture and Rural Development, 2010).
36
We also need to mention Da Hoi in Bac Ninh Province. This is a village with iron steel industries located south of Cau River and east of Hanoi, and is part of Chau Khe quarter, Tu Son district. Originally, Da Hoi was a metallic mechanical engineering professional village manufacturing household appliances. In recent time, it played also the role of recycling steel village. Its source of raw materials is mainly iron in loose bits collected from other provinces in the country. Industrial waste consists mainly of discarded scrap, iron rust, scrap iron, soil and sand, and a great amount of coal ash that results from the manufacturing process.
3. Methods 3.1. Sampling Sampling campaigns were realized in 2011 and 2012 and some stations of the 2011 survey were sampled again in 2012 in order to perform some additional analyzes. Soil and sediment samples were taken at rivers, rice fields, sewages, pounds, puddles and family wells (Fig. 2) in the Province of Bac Giang (Vietnam). Samples were taken by grab sampling or via manual collection (Fig. 3). Sediment and soil samples were kept frozen until the arrival in the laboratory and then freeze-dried and homogenised before the analysis.
3.2. Grain size Grain size analyses were carried out by wet mechanical sieving, using a sieve with 63 μm openings to separate sand and mud fraction, after a pretreatment with H2O2. Then the two fractions were dried and weighed to calculate the relative percent content.
3.3. Organic matter Organic Carbon (Corg), Total Carbon (TC) and Organic Nitrogen (ON) contents were determined using a Fisons Elemental Analyser NA2000. Prior to the analysis of the organic carbon fraction, inorganic carbonates were eliminated by pre-treatment with 1.5 M HCl.
37
Figure 2: Location of samples collected in 2011 (1-18) and 2012 (19-30). Sites 27 and 28 belong to the Bac Ninh Province.
38
d) c)
b) a)
Figure 3: Pictures of sampling areas or operations. a) well (Tu Mai), sample 17; b) Quang Chau (Dong Tien), sample 19; c) Canal collector (industrial area of Song Khe,) sample 26; d) Quang Chau (Dong Tien), sample 20.
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3.4. 137Cs Activities of gamma emitting radionuclides were obtained through gamma counting of dry samples in standard geometries with a detector coupled with an analyzer. Detection limits were set in a range between 1 and 3 Bq Kg-1.
4. Results and Discussion The purpose of the project was to evaluate the quality of the environment in the southwestern sector of the Bac Giang Province (Romanelli, this volume). Then the sampling strategy had to take into account the potential pressures and impact on the different zones and situations. Therefore the sampling campaign carried out in 2011 was focused on the definition of contaminant levels in areas not influenced by direct sources, in order to obtain a general overview on the presence of metals, As, and selected POPs in the study areas. On the contrary, the second sampling in 2012 was focused on those areas where main industrial activities are present.
Figure 4: Sand and fines percentage content for samples collected in 2011 and 2012. As for grain size composition, samples show a general high content of fines (fraction that best interact with contaminants) and only for seven of them fines content was below 50% (Table 1 and Fig. 4).
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Table 1: Samples collected in 2011 and 2012, their location and characteristic: grain size content (as % of mud and sand content), organic carbon (OC %), organic nitrogen (ON %), C/N ratio, δ13C and 137Cs (Bq kg-1) activity.
41
Table 2: Grain size content in replicate samples of the 2011 survey sample 1_r 4_r 7_r 11_r 12_r 13_r
mud % 79 98 93 78 65 67
sand % 21 1.8 7.2 22 35 33
In detail these were: sample 5 (family well: 44 %), sample 13 (family well: 29 %), sample 16 (flooding field: 37 %).17 (family well: 0.98 %); 24 (Industrial area Song Khe-Noi Hoang: 32 %); samples 27 and 28 (from Bac Nihn Province, 40 % and 30 %, respectively). Replicate samples of the 2011 survey (Table 2) showed that, with the exception of sample 1 (Hoang Ninh, Table 1), there was an enrichment of fine fractions. The soil sample 12 was the sample with less evident changes. In general variations were significant, but not so important to change the samples’ characteristics. Only the family well of Thang Cuong (sample 13, Table 1) was really different: the first sediment was mainly sandy but the second sampling retrieved a mud (from 29 to 67 % of silt plus clay). This change is impossible to explain with available information. It is possible that, by chance, the sampled wells were not the same. Like grain size, also organic matter content can affect the capability to interact with particles and contaminants. OC concentrations showed high variability, spanning the interval from 0.08 to 8.1 % (Table 1). The maximum was found in sample 28 taken at Phong Ke. Its high organic matter content and its overall composition made impossible to perform reliable analysis of organic contaminants. As a consequence, they were not determined in this sample. As expected in terrestrial environment, C/N ratio values were above 10 and ranged between 10 and 15, with the only exception of site 7, where algae input seems relevant. Furthermore δ13C ranged between -20 e -27. Fig. 5 provides information on the sources of organic matter. In particular, δ13C
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values indicates a mixed source between freshwater Dissolved Organic Carbon (DOC) and C3 plants (i.e. those organisms, including also rice, that fix CO2 producing a molecule with three carbon atoms). Samples 16, 22, 24 and 30 showed higher influence from rice fields with a C/N value characterized by low nitrogen and high carbon levels.
Figure 5: Distribution plot of C/N and δ13C
Because the Fukishima (Japan) accident happened little before our first sampling survey, analysis of
137
Cs were performed on sediment and soil
samples collected in 2011, to test the influence of radiation emission in the atmosphere on the Vietnamese territory. All samples presented activities of 137
Cs below detection limit (Table 1), thus indicating a poor influence of the
Fukushima accident. Moreover, low
137
Cs values highlight the little
influence of world nuclear experiment in the late fifties on the Vietnamese territory, as mentioned by Frignani et al. (2007), Giuliani et al. (2011) and Romano et al. (2012).
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Acknowledgements Funds for the collection and analysis of samples from the Bac Giang Province and Cau River were provided by the Italian Ministry of Foreign Affairs, Direzione Generale Cooperazione Sviluppo (DGCS), under the GVC-UCODEP project “Promotion of Environmental Quality in the Districts of Viet Yen, Yen Dung and Hiep Hoa in the Bac Giang Province, Vietnam”.The authors are grateful to M. Romanelli and G. Santavicca for the management, and to Dario Cesarini, Nguyen Thi Xuyen, Trinh Thi Thuong, Chu Bich Hanh, Duong Thi Nga Duzng, Nguyen Van Diep for help. This is contribution No. 1814 from ISMAR-CNR, Bologna.
References Bac Giang Industrial Zones Authority 2010. Bắc Giang Province: Minerals. Retrieved 29 August 2010. Bac Giang Department of Industry and Trade 2010. Bắc Giang Department of Industry and Trade tasks and powers. Retrieved 29 August 2010. Bac Giang Department of Agriculture and Rural Development. 2010. Irrigation Management Company of Bắc Giang: Water Rights and Water Allocation in Irrigation Scheme of Cầu River. Bắc Giang. Frignani M., Piazza R., Bellucci L.G.., Cu N.H., Zangrando R., Albertazzi S., Moret I., Romano S., Gambaro A., 2007. Polychlorinated biphenyls in sediments of the Tam Giang-Cau Hai Lagoon, Central Vietnam. Chemosphere, 67, 1786–1793. Giuliani S., Romano S., Turetta C., Cu N.H., Bellucci L.G.., Capodaglio G.., Mugnai C., Nhon D.H., Frignani M., 2011. Soils and sediments of the Thua Thien-Hue Province (central Vietnam): recognizing trace element sources and the likely influence of natural events. Journal of Environmental Monitoring, 13, 1383-1392. Population and Employment: General Statistics Office of the Government of Vietnam. 2010. Number of cooperatives in 2008 by kind of activity and by province: Agriculture. Forestry and Fishery.
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Population and Employment: General Statistics Office of the Government of Vietnam. 2010. Agriculture. Forestry and Fishery: Output value of agriculture at constant 1994 prices. Romanelli M. Presentation of the Project “Promotion of environmental protection in the Viet Yen, Yen Dung and Hiep Hoa districts in the Bac Giang Province, Vietnam”: implementation, strategies and results. This volume. Romano S., Mugnai C., Giuliani S., Turetta C., Cu N.H., Bellucci L.G.., Nhon D.H., Capodaglio G.., Frignani M., 2012. Metals in Sediment Cores from Nine Coastal Lagoons in Central Vietnam. American Journal of Environmental Sciences, 8, 130-142. SedNet strategy Paper, 2004. The opinion of SedNet on environmentally, socially and economically viable sediment management. European Sediment Network (SedNet), EC contract no. EVK1-CT-2001-2002, 13 pp, www.SedNet.org. Statoids "Districts of Vietnam". Retrieved 20 June 2010. Vink R., Behrendt H., 2001. Part B: Present and future quality of sediments in the Rhine catchment area – Heavy metals. In: Candrass J. Salomons W. (Eds.) Dredged material in the Port of Rotterdam - Interface between Rhine catchment area and North Sea. GKSS Geesthacht. Germany.
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Proceedings of the workshop “Environmental Quality in the Province of Bac Giang and the Cau River Basin. Perspectives for the improvement of monitoring activities and methods”. Hanoi, August 27th, 2013. Paper No. 4
Methods used for the determination of contaminants in selected soils and sediments of south-east Bac Giang Province (Vietnam) Stefano Zambon1, Clara Turetta2, Marco Vecchiato2, Rossano Piazza1,2, Silvia Giuliani3, Stefania Romano3, Giorgio Tranchida4, Luca Giorgio Bellucci3, Fabio D’Agostino4, Carlo Barbante1,2, Mauro Frignani3 1
Dept. of Environmental Sciences, Informatics and Statistics, Dorsoduro 2137, 30123, Venice, Italy
[email protected];
[email protected];
[email protected]; 2 CNR-Institute for the dynamics of Environmental processes, Dorsoduro 2137, 30123 Venice, Italy
[email protected];
[email protected] 3 CNR-Institute of Marine Sciences, Via Gobetti 101, Bologna, Italy
[email protected];
[email protected];
[email protected];
[email protected] 4 CNR-Institute of Marine Coastal Environment, Capo Granitola (TR), Italy
[email protected];
[email protected]
Tóm tắt – Phương pháp phân tích để xác định chất gây ô nhiễm (PCBs, PBDEs, PAHs, thuốc trừ sâu gốc clo, hydrocarbon, kim loại và As) trong đất và trầm tích của khu vực phía tây nam tỉnh Bắc Giang và sông Cầu (Miền Bắc Việt Nam) được thể hiện. Trong nghiên cứu này, phương pháp phân tích đồng thời mới cho PCBs, PAHs và PBDEs được trình bày, cùng với phương pháp phân tích để xác định PCDD / Fs, thuốc trừ sâu gốc clo, hydrocarbon và các yếu tố. Phương pháp US EPA đã sử dụng làm nền, và nỗ lực rất lớn đã được thực hiện để cải thiện chất lượng dữ liệu. Để tăng cường khả năng lặp lại và giảm nguy cơ ô nhiễm, dụng cụ tự động đã được sử dụng để chiết xuất các hợp chất hữu cơ (PLE, ASE) và, khi có thể, để dọn dẹp (Power Prep), tất cả phân tích mang tính công cụ được thực hiện thông qua kỹ thuật khối phổ (HRGC-LRMS, HRGC-HRMS, ICP-QMS). Abstract – Analytical methods relative to the determination of contaminants (including PCBs, PBDEs, PAHs, chlorinated pesticides, hydrocarbons, metals and As) in soils and sediments of the southwestern Bac Giang province and the Cau River (northern Vietnam) are presented. In this study, a novel simultaneous analytical method for PCBs, PAHs and PBDEs is presented, followed by analytical methods for the determination of PCDD/Fs, chlorinated pesticides, hydrocarbons and elements. US EPA methods were used as template, and a great effort was done in order to
47
improve data quality. In organic compound investigations automated instruments were used for sample extraction (PLE, ASE), and when possible for cleanup step (Power Prep), in order to enhance repeatability and reduce contamination risks. All Instrumental analysis were done via mass spectrometry technique (HRGC-LRMS, HRGC-HRMS, ICP-QMS). Keywords: POPs, Hydrocarbons, Minor and Trace Elements, Sediment, Soil.
1. Introduction The aim of this work is to summarize the analytical methods used in some of the works presented in this volume (Giuliani et al., this volume; Piazza et al., this volume; Turetta et al., this volume), concerning the determination of POPs, hydrocarbons, and trace metals in soils and sediments of the southwestern Bac Giang province (Vietnam). Sampling details are discussed by Romano et al. (this volume). In this study, the following classes of chemicals listed as persistent organic pollutants (POPs) are considered: polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons
(PAHs),
polybrominated
diphenyl
ethers
(PBDEs),
polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs). Other analyzed organic compounds included chlorinated pesticides and hydrocarbons. Moreover, the analytical method for the analysis of minor and trace elements is presented. All these analyses were performed by laboratories of italian research institutes: CNR-ISMAR of Bologna, CNR-IDPA of Venice, DAIS - Ca’ Foscari University of Venice and IAMC-CNR UOS of Capo Granitola (TR). In the following paragraphs each analytical method is described in detail.
2. PCBs, PAHs, PBDEs We developed a new method in order to determine PCBs, PAHs, and PBDEs with the same sample preparation protocol. This analytical method was built up with reference to EPA, literature methods for POPs in sediments and soils (Frignani et al., 2006; Piazza et al., 2009; Piazza et al., 2010; Giuliani et al., 2011a; Romano et al., 2013) and a method recently
48
developed to determine different POPs classes simultaneously in air (Piazza et al., 2013). Automated instruments were used for sample extraction and cleanup in order to enhance repeatability and reduce contamination risks. Unlike most common approaches, no separation of the analytes was performed before the GC analysis in order to avoid sample fractionation and to save time and materials.
Table 1: List of determined congeners of PCB. Coeluted compounds with the same mass value are listed with “+” sign (i.e. 10+4 means PCB 10 coeluted with PCB 4). n° chlorine
n° congeners
1
3
1, 2, 3
2
10
10+4, 7+9, 6, 5+8, 11, 12, 15
3
17
19, 18, 17, 24+27, 16+32, 29, 34, 26, 25, 31, 28, 20+33, 22, 37
23
45,46, 69, 52, 49, 47+48, 44, 42+59, 71+41+64, 40, 67, 63, 74, 70, 66, 56+60, 81, 77
24
104, 103, 93+95, 91, 92, 84+90+101, 99, 119, 83, 97, 87+115, 85, 110, 82, 107, 123, 118, 114, 105, 126
22
136, 151, 135+144, 147, 149, 134, 131, 146, 153, 132, 141, 137, 138+164, 158, 129, 128+167, 156, 157, 169
7
17
179, 176, 178, 187, 183, 185, 174, 177, 171, 173, 172, 180, 193, 191, 170+190, 189
8
7
197, 199, 196+203, 195, 194, 205
9
3
208, 207, 206
10
1
209
4
5
6
PCB
Compound investigated were: a) 127 of 206 PCBs, including monoortho and non-ortho dioxin like compounds, PCB 11, indicators and congeners tipycally found in Aroclor mixtures (Table 1); b) 15 of 16 priority PAHs (Naphtalene was not determined); c) 14 PBDEs, typically found in commercial mixture (Table 2).
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Table 2: List of determined congeners of PBDE. n° bromine
n° congeners
PBDE
3
2
17, 28
4
3
71, 47, 66
5
3
100, 99, 85
6
3
153, 154, 138
7
2
183,190
10
1
209
The following describes the analytical procedure. Extraction of samples was performed with a PLE extractor (FMS, Fluid Management System Inc.) equipped with stainless steel extraction cells. Approximately 3 g of dried samples were mixed with activated copper, anhydrous sodium sulphate and diatomaceous earth (Applied Separations Inc.), then placed in the cell and covered with Ottawa Sand (Applied Separations Inc.). The extracting solvent was n-hexane–dichloromethane (1:1, v/v) and the operating conditions of the extractor were the following: extraction temperature 100 °C, extraction pressure 1500 psi, static extraction 7 min and number of extraction cycles 3. After extraction, samples were spiked with a known amount of isotopically labelled compound solutions (Table 3). Table 3: List of 13C labelled congeners used as quantification standard. C PCB
3, 15, 28, 52, 77, 81, 105, 114, 118, 123, 126, 153, 156, 157, 167, 169, 180, 189, 194, 208, 209
C PAH
Acenaphthene, Phenanthrene, Benzo(a)pyrene
13
13
13
C PBDE
28, 47, 100, 99, 153, 183
After volume reduction to 500 μL with a gentle nitrogen flow at 23 °C (Turbovap II, Caliper Life Science), the extract was made up to 5 mL with n-hexane and reduced again to 500 μL. Samples were then made up to 2 mL with n-hexane and transferred in a glass syringe for injection in the automated cleanup system (PowerPrep, FMS). Cleanup was performed by
50
direct injection of the sample onto a disposable neutral silica column (FMS), eluted with 30 mL of n-hexane (10 mL min−1) followed by 30 mL of nhexane–dichloromethane (1:1, v/v; 10mL min−1). Determinations were conducted with a quadrupole mass spectrometer (Agilent Technologies 5975C) operating in electron impact mode (EI, 70 eV), coupled with an Agilent Technologies 7890A gas chromatograph. Acquisition was performed using selected ion monitoring (SIM). The gas chromatographic separation was executed on a 60-m HP-5MS column (0.25 mm I.D., 0.25 μm; Agilent Technologies) for PCBs and PAHs, while a 15-m column of the same type was used for PBDEs. Quantification was performed using internal standards and the isotopic dilution technique. Results were corrected using the instrumental response factor. In most important samples, PCB analyses were also carried out on a MAT 95XP high-resolution magnetic mass spectrometer (ThermoFinnigan) in electron impact mode (EI, 45 eV), working at resolution of 10000 in Multiple Ion Detection (MID), coupled with a Hewlett Packard-Agilent 6890 Series GC System mounting the same 60 m column described above.
3. PCDD/Fs The analysis of PCDD/Fs was implemented starting from the USEPA 1613 method for the determination of 17 priority congeners (Table 4), improved with automated instruments (Piazza et al., 2010). PCDD/Fs were analysed in some selected sediment and soil surficial samples. Freeze-dried samples were extracted three times (7 min) with toluene, at temperature of 130°C and pressure of 1500 psi in a PLE extractor (FMS), in presence of anhydrous Na2SO4 and activate copper. The extract was then additionated of an EDF 8999 solution (Cambridge Isotope Laboratories) containing 15 13Clabeled PCDD/F congeners as internal standards. After volume reduction to 2 mL in n-hexane, as explained in the previous chapter, the clean-up was performed using the automatic system Power Prep (FMS). Samples were eluted with solvents through two prepacked disposable columns containing multilayer silica and alumina, respectively.
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Table 4: List of determined congeners of PCDD/Fs. n° chlorine
n° congeners
4
2
2,3,7,8-TCDD; 2,3,7,8-TCDF
5
3
1,2,3,7,8-PeCDD; 1,2,3,7,8-PeCDF; 2,3,4,7,8-PeCDF
6
7
1,2,3,4,7,8-HxCDD; 1,2,3,6,7,8HxCDD; 1,2,3,7,8,9-HxCDD; 1,2,3,4,7,8-HxCDF; 1,2,3,6,7,8HxCDF; 1,2,3,7,8,9-HxCDF; 2,3,4,6,7,8-HxCDF
7
3
1,2,3,4,6,7,8-HpCDD; 1,2,3,4,6,7,8HpCDF; 1,2,3,4,7,8,9-HpCDF
8
2
OCDD; OCDF
The
high
resolution
gas
PCDD/F
chromatography–mass
spectrometry
(HRGC/HRMS) analyses were carried out using a gas chromatograph Agilent G6890 Series GC System coupled to a MAT 95XP mass spectrometer (ThermoFinnigan) operating in EI mode at 45 eV. Acquisition was performed using MID (Multiple Ion Detection) at the resolution of 10000. Quantification was performed using internal standards and the isotopic dilution technique. Results were corrected using the instrumental response factor.
4. Chlorinated Pesticides Investigated compounds were: 4,4’DDD, 4,4’DDE, 4,4’DDT Aldrin, Dieldrin, Endosulfan α, Endosulfan ß, Endosulfan solfate, Endrin, Endrin aldehyde, Eptachlor, Eptachlor eso-epoxide, Exachlorocycloexane α, Exachlorocycloexane ß, Exachlorocycloexane γ, Fenclorim, Metoxichlor, PCNB, Pretilachlor and Trichlorophenol. Analyses were performed following US EPA methods 3545 and 3620, for extraction and purification, respectively. Briefly, 5 g of freeze-dried sample were extracted via an accelerated solvent extractor (ASE 200, Dionex) by hexane/acetone mixture (80:20 v/v). After volume reduction, the extract was made up to 0.5 mL with an hexane/isooctane mixture (1:1 v/v) and then purified with 1g Florisil
52
chromatographic column, using 20 mL of hexane/isooctane mixture (1:1 v/v). Eluate was then concentrated and made up with dichloromethane and mixed with mercury. This solution was then filtered by a Na2SO4 column, in order to remove the precipitated HgS, using pentane as eluent. The GC-MS analyses were carried with a DB5 column and acquisition was performed using selected ion monitoring (SIM). Quantification was determined via calibration curve and using pentachloronitrobenzene as internal standard.
5. Hydrocarbons Analysis for the determination of Total Petroleum Hydrocarbon in sediments and soils investigated the range from C12 to C35, covering in this way most of Diesel Range Organics (DOR) and Oil Range Organics (ORO). Methods used comply with EPA 3545A for extraction, EPA 3620 for cleanup and EPA 8270D for qualitative and quantitative analysis using GC/MS. Protocol of analysis was as follows. About 5 grams of sample were mixed with Extrelut NT and dried Na2SO4. The ASE cell was filled with, in order: a glass fiber filter, one little spoon of dried Na2SO4, and finally the sample, as suggested by Dionex. The extract (about 30 mL) was reduced to 2-3 mL using a rotary evaporator and made up to 5 mL with hexane. The extract was then cleaned up with SPE Lichrolut EN (0.5 g / 6 mL, VWR), which is similar to SPE Florisil but with a greater surface area. Prior to sample injection, SPE cartridge was conditioned with 5 mL of acetone and 2 mL of hexane, and sample was eluted with 6 mL of hexane. The eluted fraction was then dried under a gently nitrogen flow and the residue recovered with 1 ml of hexane with 10 ppm of 5-alfa-androstane used as internal standard. Instrumental analysis was conducted with the injection on a GC/MS instrument (Focus GC coupled with DSQ II mass spectrometer, Thermo Fisher), with a 30 m DB5-MS capillary column. Acquisition was performed using selected ion monitoring (SIM).
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6. Metals For the analyses of trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl, U, V, Zn) in soils and sediments, aliquots of 0.5 g were extracted under reflux with 10 mL of HNO3 8 N and 3 mL of H2O2 30%, at 120 °C for two hours (modified from Bellucci et al., 2002). This procedure allows the dissolution of elements bound to Fe–Mn oxides, carbonates and OC, all fractions that are likely available to the living biota; the surficial part of mineral grains is also leached, but the lattices remain untouched (Giuliani et al., 2011b). The resulting solutions were centrifuged, diluted to 100 mL with Milli-Q water and then analysed by ICP-QMS (Agilent 7500) fitted with a standard double-pass spray chamber and a v-groove nebulizer (RF power 1400 W, sample gas 1.20 L min−1, sample flow rate 500 mL min−1, dwell time 20 ms, and 3 points per peak).
7. Data Quality Each analytical method here presented was investigated in order to assure a good precision and accuracy.
Figure 1: Comparison of PBDEs concentration found in duplicate analysis of PBDE/PCBs in soil, Number SQC072 SRM (indicated as SRM(a) and SRM(b)) and certified values with associated error (indicated as Certified). Precision was measured as standard deviation of results in different analysis of the same sample. Accuracy was estimated through the analysis
54
of suitable standard reference materials (SRMs) and comparing the obtained values with the certified ones. The analysed SRMs were: NIST2711a (metals), DX1 - National Water Research Institute (PCDD/Fs, Pesticides), NIST SRM 1941b (PCBs, PAHs) and PBDE/PCBs in Soils, Number SQC072 (PCBs, PBDEs). As an example, Figs. 1 and 2 show accuracy result for PCBs and PBDEs analysing SQC072 SRM.
Figure 2: Comparison of PCBs concentration found in duplicate analysis of PBDE/PCBs in Soil, Number SQC072 SRM (indicated as SRM(a) and SRM(b)) and certified values with associated error (indicated as Certified).
Acknowledgements Collection and analysis of samples were funded by the Italian Ministry of Foreign Affairs, Direzione Generale Cooperazione Sviluppo (DGCS) under the GVC-UCODEP project “Promotion of Environmental Quality in the Districts of Viet Yen, Yen Dung and Hiep Hoa in the Bac Giang Province, Vietnam“. The authors are grateful to M. Romanelli and G. Santavicca for the management, and to D. Cesarini, Nguyen Thi Xuyen, Trinh Thi Thuong, Chu Bich Hanh, Duong Thi Nga Duzng, Nguyen Van Diep for help. This is contribution No. 1815 from ISMAR-CNR, Bologna.
References Bellucci L.G., Frignani M., Paolucci D., Ravanelli M., 2002. Distribution of heavy metals in sediments of the Venice Lagoon: the role of the industrial area. Science of the Total Environment, 295, 35-49.
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Frignani M., Piazza R., Bellucci L.G., Cu N.H., Zangrando R., Albertazzi S., Moret I., Romano S., Gambaro A., 2006. Polychlorinated biphenyls in sediments of the Tam Giang-Cau Hai Lagoon, Central Vietnam. Chemosphere, 67, 1786-1793. Giuliani S., Piazza R., Bellucci L.G., Cu N. H., Vecchiato M., Romano S., Mugnai C., Nhon D. H., Frignani M., 2011a. PCBs in Central Vietnam coastal lagoons: Levels and trends in dynamic environments. Marine Pollution Bulletin 62, 1013–1024. Giuliani S., Romano S., Turetta C., Cu N. H., Bellucci L.G., Capodaglio G., Mugnai C, Nhon D. H., Nhon D. H., Frignani M., 2011b. Soils and sediments of the Thua Thien-Hue Province (central Vietnam): recognizing trace element sources and the likely influence of natural events. Journal of Environmental Monitoring, 13, 1383-1392. Giuliani S., Piazza R., Zambon S., Vecchiato M., Polo F.P., Romano S., Bellucci L.G., Frignani M. Polycyclic Aromatic Hydrocarbons in samples from the southwestern Bac Giang Province and the Cau River (northern Vietnam). This volume. Piazza R., Moumni B. E., Bellucci L.G., Frignani M., Vecchiato M., Giuliani S., Romano S., Zangrando R., Gambaro A., 2009. Polychlorinated biphenyls in sediments of selected coastal environments in northern Morocco. Marine Pollution Bulletin, 58, 424–455. Piazza R., Giuliani S., Bellucci L.G., Mugnai C., Cu N. H.,Nhon D. H., Vecchiato M., Romano S., Frignani M., 2010. PCDD/Fs in sediments of Central Vietnam coastal lagoons: In search of TCDD. Marine Pollution Bulletin, 60, 2303–2310. Piazza R., Gambaro A., Argiriadis E., Vecchiato M., Zambon S., Cescon P., Barbante C., 2013. Development of a method for simultaneous analysis of PCDDs, PCDFs, PCBs, PBDEs, PCNs and PAHs in Antarctic air. Analytical and Bioanalytical Chemistry, 405, 917–932. Piazza R., Zambon S., Giuliani S., Romano S., Tranchida G., Bellucci L.G., Vecchiato M., D’Agostino F., Frigani M. PCBs, PBDEs, PCDD/Fs, chlorinated pesticides and hydrocarbons in soil and sediments from
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the Bac Giang Province and the Cau River (northern Vietnam). This volume. Romano S., Piazza R., Mugnai C., Giuliani S., Bellucci L.G., Cu N. H., Vecchiato M., Zambon S., Nhon D. H., Frignani M., 2013. PBDEs and PCBs in sediments of the Thi Nai Lagoon (Central Vietnam) and soils from its mainland. Chemosphere, 90, 2396–2402. Romano S., Giuliani S., Bellucci L.G., Frignani M. Promotion of Environmental Quality in the Districts of Viet Yen, Yen Dung and Hiep Hoa in the Bac Giang Province, Vietnam: sediment and soil samples for environmental quality assessment. This volume. Turetta C., Corami F., Romano S., Giuliani S., Frignani M. Distribution and risk assessment of minor and trace elements in soils and sediments from the Cau River Basin (Bac Giang Province, Northern Vietnam). This volume.
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Proceedings of the workshop “Environmental Quality in the Province of Bac Giang and the Cau River Basin. Perspectives for the improvement of monitoring activities and methods”. Hanoi, August 27th, 2013. Paper No. 5
Distribution and risk assessment of minor and trace elements in soils and sediments from the Cau River Basin (Bac Giang Province, Northern Vietnam) Clara Turetta1, Fabiana Corami1, Stefania Romano2, Silvia Giuliani2, Luca Giorgio Bellucci2, Mauro Frignani2, Carlo Barbante1,3 1
CNR-Institute for the Dynamics of Environmental Processes, Dorsoduro 2137, 30123 Venice, Italy
[email protected];
[email protected];
[email protected] 2 CNR-Institute of Marine Sciences, Via Gobetti 101, Bologna, Italy
[email protected];
[email protected];
[email protected];
[email protected] 3 Dept. of Environmental Sciences, Informatics and Statistics, Dorsoduro 2137, 30123, Venice, Italy
Tóm tắt – Kết quả phân tích của Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl, U, V, và Zn trong 30 mẫu từ đất và trầm tích của phía tây nam Bắc Giang được thảo luận. Một số giá trị tương đối cao đôi khi vượt quá Nguyên tắc Chất lượng Trầm tích Dựa trên cơ sở Đồng thuận (CB-SQGs). Điều này có nghĩa rằng các phần tử nhỏ và dấu vết có thể là một mối đe dọa cho các sinh vật tại nhiều địa điểm, đặc biệt là As, cũng như Zn, Ni, Mn và Fe vượt quá tiêu chuẩn quốc tế ở một số địa điểm. Nguồn gốc giả thuyết đề nghị sự đóng góp tự nhiên đến mức cao của các yếu tố nhất định. Mặc dù vậy, nồng độ cao của chất gây ô nhiễm, mặc dù nguồn gốc tự nhiên có thể là một vấn đề đặc biệt là giếng dùng cho mục đích uống. Vì lý do này chỉ số rủi ro sinh thái tiềm năng (RI) cũng được coi là đánh giá tốt hơn các mối nguy hiểm sinh thái tiềm năng của các yếu tố được nghiên cứu trong đất và trầm tích của khu vực. Abstract – Results of the analyses of Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl, U, V, and Zn in 30 samples from soils and sediments of the southwestern Bac Giang Province are discussed. Some values are relatively high, sometimes exceeding the Consensus Based Sediment Quality Guidelines (CB-SQGs). This means that minor and trace elements can be a threat for organisms at many sites, especially As. However, also Zn, Ni, Mn and Fe exceed the lower international benchmark at several locations. Hypothetical backgrounds suggest a natural contribution to high levels of certain elements. Despite this, the high concentration of contaminants, although of possible natural origin, is a problem especially for wells used for drinking purposes. For this reason also potential ecological risk index (RI) is
59
considered to better evaluate the potential ecological hazard of studied elements in soils and sediments of the area. Keywords: metals, As, soils, sediments, Bac Giang province, northern Vietnam
1. Introduction Toxic elements in soils and sediments represent a global problem especially in absence of the implementation of sustainable development policies and effective environmental control and management. To correctly plan the development of an anthropised area, and to safeguard environmental quality, it is fundamental to identify contaminant sources and carefully evaluate the potential risks for both organisms and people. In this context, the analysis of sediments represents a good source of information because contaminants tend to interact with particles and accumulate onto the bottom of water bodies. Sediments are also useful to study changes over time. Furthermore, soils can provide insight on the widespread diffusion of chemicals. Trace metals and As are an important class of contaminants that may derive from a number of natural and anthropogenic sources. The Cau River may transport chemicals from mines and manufacturing activities located in the northern provinces, and also the Bac Giang Province itself, due to its important social and economical development, may be one cause of contamination. Furthermore, the nearby Bac Ninh Province may also have a role, because of the presence of important craft villages. In spite of this, the so far available data are not sufficient to evaluate the risks for the environment. The purpose of this work was to provide data to expand the knowledge about the contamination of different environments in the territories of the communes of Van Ha, Hoang Ninh, Yen Lu, Thang Cuong and Tu Mai in the southwestern Bac Giang province (Romanelli, this volume; Romano et al., this volume). The Enrichment Factor and the Potential ecological risk index were used to evaluate the pollution status of
60
the area and asses the potential ecological risk of major and trace elements analysed.
2. Methods Sixteen elements (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl, U, V, and Zn) were analysed in 30 samples (soils and sediments) collected during two sampling campaigns in 2011 and 2012 (Romano et al., this volume). This is an important group of contaminants that may derive from a number of natural and anthropogenic sources. The method is described in detail by Zambon et al. (this volume).
3. Results and discussion Table 1 reports average, minimum and maximum concentration for the sixteen elements measured on sediment and soil samples. Most samples (23 out of 30) are prevalently fine (silt plus clay > 50%), with seven exceptions in which the sand fraction is prevalent (> 50%; Romano et al., this volume).
Table 1: Average, minimum and maximum concentrations measured on collected samples.
Average Min Max
Average Min Max
Al
As
Cd
Co
Cr
Cu
Fe
Hg
µg g-1
µg g-1
µg g-1
µg g-1
µg g-1
µg g-1
µg g-1
µg g-1
10752 2501 24565
20 3.2 77
0.31 0.01 1.1
12 1.7 51
36 16 71
23 0.20 73
29281 9859 60336
0.18 0.01 0.99
Mn
Ni
Pb
Sb
Tl
U
V
Zn
µg g-1
µg g-1
µg g-1
µg g-1
µg g-1
µg g-1
µg g-1
µg g-1
375 27 1579
22 1.9 76
40 7.8 89
0.31 0.03 4.1
0.30 0.10 2.6
2.1 0.50 12
40 14 96
100 10 549
The state of contamination of the studied area was evaluated by assessing a probability for the occurrence of adverse biological effects in organisms due to their interaction with contaminants. Sediment Quality Guidelines (SQGs) were developed empirically using different statistical methods on the basis of the observed associations between large data sets of
61
measured adverse biological effects and the concentration of potentially toxic substances present in the environment (Suter II, 1995; Long et al., 1995; MacDonald et al., 2000). Recently, it was recognised that elevated contaminant levels might not be sufficient for the occurrence of adverse effects (Peijnenburg and Jager, 2003), since specific combinations of chemical, biological, and environmental parameters determine both bioavailability and bioaccessibility. To partially overcome this problem, in this study, a leaching procedure has been used to determine the bioavailability of trace elements (Zambon et al., this volume). Moreover, SQGs in this study were used just as a preliminary screening tool to assess the potential biological significance of sediment-bound contaminants in the absence of direct biological effects data. Threshold effect concentration (TEC) and a probable effect concentration (PEC) have been considered for each contaminant of concern (MacDonald et al., 2000). The results of this evaluation are reported in Fig. 1: As, Pb, Hg, Cu, Cr, Zn, Cd exceed their TEC levels in 9, 11, 8, 8, 8, 6, and 1 cases, respectively. Only As and Zn exceed their PEC levels in 4 and 1 cases, respectively. Based on this information we could conclude that soils and sediments are significantly contaminated by elements such as As, Pb, Hg, Cu, Cr and Zn, but not by others (Cd, Sb). Before reaching such a conclusion, however, it is necessary to carefully assess the geology of the area in order to define local background levels, especially when analysing soil samples (Reimann and Garrett, 2005). In fact, the literature reports very high concentrations of Pb, As, Zn, Mn and Cd in samples collected in various provinces of North Vietnam (Ha et al., 2011; Mai and Pham, 2003). In this study we used the Enrichment Factor (EF) (Duce et al., 1972; Lawson and Winchester, 1979; Sugawara, 1965) to asses the level of contamination and the possible anthropogenic impact in the collected samples. The EF is defined as follows (Ergin et al., 1991):
EF = (M M ce )sample (M M ce )background
62
where
is the ratio of the element and a conservative element
concentrations in the same sample, and in a background material, respectively.
As
Cu 90
160
80
140
70
120 -1 µg g
-1 µg g
60 50 40
100 80 60
30
40
20
20
10 0
0 1
2
3
4
5 6
7
8
1
9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 29 30
2
3
4
5 6
7
8
samples
Fe
samples
Pb
70000
160
60000
140 120 -1 µg g
-1 µg g
50000 40000 30000
100 80 60
20000
40
10000
20
0
0 1
2
3
4
5 6
7
8
9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 29 30
1
2
3
4
5 6
7
8
samples
Mn
Cr 120
1600
100
1400
80 -1 µg g
-1 µg g
1200 1000 800 600
60 40
400
20
200 0
0 1
2
3
4
5
6 7
8
9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 29 30
1
2
3
4
5 6
7
8
Zn
9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 29 30 samples
samples
Cd 600
6
500
5
400
4 -1 µg g
-1 µg g
9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 29 30 samples
1800
300 200
3 2
100
1
0
0 1
2
3
4
5 6
7
8
9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 29 30
1
2
3
4
5
6
7
8
samples
Hg
9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 29 30 samples
Sb 1.2
30
1
25
0.8
20 -1 µg g
-1 µg g
9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 29 30
0.6 0.4
15 10
0.2
5
0
0 1
2
3
4
5 6
7
8
9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 29 30
1
samples
2
3
4
5 6
7
8
9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 29 30 samples
Ni 80 70
-1 µg g
60 50 40 30 20 10 0 1
2
3
4
5 6
7
8
9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 29 30 samples
Figure 1: Pollutant concentrations compared with TEC (red line) and PEC (green line) limits.
63
Generally, a normalization with respect to a conservative element (e.g. Al, Fe, or Si) is used to identify anomalous concentrations in the samples. Al was chosen because it is scarcely affected by anthropogenic inputs. As a first approximation, EF values were calculated with respect to upper continental crust (UCC) average (Wedepohl, 1995). EF
