PROJECT PRESENTATION

Key words:

 water quality, heavy metals, total organic carbon (TOC), dissolved organic carbon (DOC), trihalomethanes (THM)

 
Project summary

The water problem is more and more acute in our country and in the world. Resources exploitation and pollution grew continuously, so that the quantitative and qualitative water supply for the human collectivities, in spite of the uppermost efforts at national and international level, is far for being resolved. The water of Terra is a constant quantity that we are not able to influence, in opposition with other resources, which can be theoretically multiplied or other like fossil combustibles which are constantly reduced by consumption. But we can alter its quality and that’s what we are full doing. The science is demonstrating that abusing of water we harm other species, the nature and generally the environment. Abusing of water quality and quantity is, in fact causing an injury we to ourselves and above all to the next generations. To have the desired water without compromising the sustainable development, we have first to know and understand it.

The industrialization, the use of chemical fertilizers and pesticides in agriculture, as well as the natural degradation of dead plants and animals have negative effects on the quality of water. This becomes loaded with nitrates and a large variety of organic compounds, most of them with toxic effect. The quantity of natural organic matter is estimated by the determination of the “total organic carbon” (TOC) and of the “dissolved organic carbon” (DOC).

The heavy metals are not degradable and exceeding particular concentrations – often very low – represent a risk for the living organisms. They have the tendency to accumulate in the living matter. Thus, the contamination level increases for the organisms situated on the upper side of the trophy chain. NOM is a complex material constituted of substances with various chemical and physical properties, resulting from the photosynthesis. It is formed by compounds with small molecules like hydrophilic acids, proteins and amino-acids, but also from very large molecules like humic flivic acids. An important characteristic of NOM is his capacity to form bonds with metals controlling in this way their toxicity in water.

Romania is a country with poor water resources. In spite of many accumulations, the volume of surface still waters is modest and the rivers have small volumetric flow rates. Numerically, the total water resources of Romania are evaluated at 40 x 10⁹ m³/year, from which, in interior rivers only 5 x 10⁹ m³/year and 3 x 10⁹ m³/year underground water. The hydric potential is estimated at 1750 m³/inhabitant/year, versus the European average of 4800 m³/inhabitant/year. Thus, Romania has all the reasons to care about his waters, which raise serious problems not only quantitatively but also qualitatively.

This project proposes a high sensitivity investigation of the quality of some surface waters used for human consumption over an area extended to two counties in northwest Transylvania: Cluj and Sălaj. The main objective of the investigation is represented by the heavy metals present at trace level, the organic carbon and the disinfection products. Trace determinations of rare earth elements (REE) solvated in water will be correlated with the study of their concentration in soil and sediments. Investigations will be done on precipitation water too, in order to determine the way of penetration of heavy metals pollutants in water and the dynamics of organic and inorganic pollutants correlated with the water origin in studied systems.

The scope of the project

During the treatment of the raw water, from the reaction of NOM with the chloride, the disinfection products appear and among them trihalomethanes (THM), a group of volatile organic compounds dangerous for the human health. Water is a source for Ca, Mg, Na, K and other benefic substances for the organism, but sometimes it carries also undesired elements. There are substances which can harm over a threshold concentration. Others create problems if they are in too small concentration. Finally, there are substances that can harm at any concentration. Our project aims the metals and the dissolved organic matter, particularly the heavy metals. Among these, cadmium (Cd), mercury (Hg) and lead (Pb) are considered to be of the most harmful.

Systematic observations will be carried out, on a long time period, in correlation with the climatic conditions. Determinations of traces of REE solvated in water will be correlated with the study of their concentration in soil. Investigations will be done on the meteoric water in order to establish the way of penetration of the heavy metal pollutants in water. Determinations of isotopic ratios ¹H/D, ¹³C/¹²C for the dissolved carbon, ¹⁸O/¹⁶O will allow to establish the origin and the dynamics of water from the lakes used to prepare the drinking water. Determination of TOC, DOC and THM will be done simultaneously with the study of the THM formation kinetics during the disinfection process in the presence of traces of heavy metals. The scope is the determination of the mechanism leading to the penetration of elements at trace level with toxic potential in the water delivered to great urban agglomeration from the counties of Cluj and Sălaj.

Project description - scientific and technical description S/T current stage in the field, at national in international level

According to the World Health Organization, about 2/3 of the getting ill cases have the cause in polluted water. In Romania by the adhering at the European Union, the European regulations concerning the quality of water are mandatory [1].

            At national level there are few studies concerning heavy metal pollution of waters. We mention:

▪ M. Matache et al [2] by an ICP-OES technique made simultaneous determination on 18 elements in a water treatment station in Brasov. it was found that Fe exceeds by 30% the limits [3].

▪ A. Pamula et al [4] made determinations on samples from surface waters and from water treatment stations from Sălaj county by an ICP-MS method. 24 elements were investigated simultaneously. Mn and Fe were found in excess

▪ D. Ristoiu et al [5] made THM determinations on waters destined to the consumption in four water treatment stations (Cluj, Dej, Beclean, Jibou).

▪ Cristina Mihaela Barbu et al [6] presented a comparative study for two investigation methods of the traces of heavy metals in the rivers Jiu and Olt.

At international level a United Nations program for a Global Environment Monitoring System (GEMS) is active. In the frame of this system, the concentration of heavy metals is a compulsory parameter to assess the quality of water. There are an increasing number of studies and researches concerning the characterization of water referring to the pollution and the risks encountered by the population because of it. For instance:

▪ J. Mannio et. al [8] publishes a study concerning elements at trace level in lakes from Lapland. The elements particularly targeted were Cd, Pb, As, Ni, Cu, Cr, Y, Al.

▪ Lennart Weltje et al [9] study the correlation between the lanthanides concentration in some surface waters and their accumulation in plants and aquatic living beings.

▪ A. Concas et al [10] study the mobility of heavy metals from tailings to stream waters in a mining activity contaminated site

▪ Zhi-Yong Huang et al [11] rapport data regarding bioaccumulation of Cd, Hg and Pb in some fish organs.

▪ L. Halicz et al [12] use ICP-MS methods for the characterization of natural water resources from Israel. And the list could continue.

The presence of NOM in the water treatment stations leads to the clogging of the membranes or to the saturation of the ion exchange resins [13 - 16] causing an altering of water quality. The mechanism of complexation with ions of different metals is not very well known [17] and the interaction of NOM with metallic ions affects the degree of its removing from the raw water and also its solubility, toxicity and may be, the biostimulating properties of the trace elements [18, 19]. The reactive components of NOM interact also with organic and inorganic pollutants modifying their toxicity and solubility. This interaction is due to the ability of the functional groups of NOM to replace water molecules with metals or to form new bonds with them [20]

 Contribution of the project to the development of the knowledge in the specific field

 The project proposes the development of modern analytical methods, in agreement with UE regulations, for the determination of the content in heavy metals by inductively coupled plasma mass spectrometry and the establishment of the mechanism of penetration of these elements in water. The most significant elements present at trace level in the water supplied as drinking water, and also the content of waste waters and the treated wares before their release in rivers will be determined. We mean mainly the heavy metals Pb, Cd, Hg, etc., as well as the fraction of the organic pollutants evaluated by TOC and DOC.

The novelty consists in the association of several analytic methods of high sensitivity – isotope ratio mass spectrometry (IRMS), inductively coupled plasma mass spectrometry (ICP/MS), the coupling gas chromatograph – mass spectrometer (GC-MS) – to find out the dynamics of the migrations of contaminants, while precedent studies aimed preponderantly a static observation of the phenomenon.

Stable isotopes have frequently been used to determine the origins of organic matter in sediments. In addition the stable isotopes of hydrogen oxygen, carbon, and nitrogen have provided a means to trace the flow and fate of sewage and other anthropogenic effluents. Water in a river may be originating from different sources of specific isotopic content (¹⁸O and ²H). The origin of water may be correlated with its isotopic composition of O and H. The d¹³C values for the dissolved organic carbon lie between -18‰ and -46‰. Knowing the isotopic composition of the sources of organic carbon influencing an environment it is possible to establish quantitatively their relative contribution.

A comparison will be made between the quality of water at the entrance of the distribution system and that observed at the domestic consumer, to evidence possible contamination sources – caused by the technical condition of the distribution system: lead may reach the water from the old lead pipes, from the zinc-coated pipes Zn and sometimes As may reach the water. Bio films may also appear maintaining NOM and consequently the THM.

The variation of the measured concentration will be observed in connection with the meteorological conditions (precipitations, temperature) and will be corroborated with measurements on meteoric waters. Waste waters will also be analyzed before the treatment and after the treatment before the release in river.

Ultra-trace determinations for REE from sediments, soil, correlated with isotope ratio measurements ¹H/D and ¹⁸O/¹⁶O will allow determining the origin of the studied waters.

Measurements of TOC, DOC and THM through specific techniques, as well as molecular kinetics studies concerning the chloride interaction with NOM leading to THM, will be realized.

Analytical methods for the determination of heavy metals in matrices like: soil, sediments, vegetal tissues will be developed and validated. Samples with total dissolved solid over 0.2% will be processed by the flow injection technique and by HPLC/ICP-MS coupling speciation will be achieved for different valence states.

The geographical zones targeted are the counties Cluj and Sălaj.

Preliminary measurements [4] realized on samples collected from 7 locations from Sălaj county confirmed the presence of heavy metal (like Cd, Pb, Mn, Cr, Fe, Se and others) traces in water. Water samples from the Someş river (unpublished results), collected from Cluj-Napoca, evidenced Pb (1,2 µg/l), Cd (0,064 µg/l), Cr (2,4 µg/l), Cu (6,7 µg/l), Ni (2,5 µg/l), Mn ( 10,5 µg/l) and others. Analyses performed on water samples collected from domestic consumers showed the presence of lead in the „drinking” water, at a concentration 400 times greater then the limits stated by the UE regulations (stated limit 10 µg/l and 460 µg/l were found) in a building with an old lead made pipe system. With few exceptions these concentrations are well under the limits stated by regulations.

Bibliography & References:

[2].M. Matache, Mariana Ropotă, C. Pătroescu, Deteminarea unor metale grele din apele uzate de la staţia de epurare din Braşov (Rev. Chim. 54. 3. 2003)

[3].Monitorul oficial 303 bis. 7 Nov. 1997 – NTPA001 / 1997 „Normativul privind stabilirea limitei de încărcare cu poluanţi a apelor uzate evacuate în resursele de apă”

[4].Pamula, Cezara Voica, R. Chira şi C. Cuna: Heavy Metal Traces in Some Surface Waters from Northwest Transylvania  5-th Conference on Isotopic and Molecular Processes, Cluj – Napoca, 20 – 22 Sept. 2007 (Proceedings to be published in Rev. Chim. 2008).

[5].Culea Monica, Cozar Onuc and Ristoiu Dumitru, Method validation for the determination of trihalomethane in drinking water, J. Mass Spectrom.2006;41:1594-1597.

[6].Cristina Barbu, Anişoara Preda, A. Popescu şi D. Selişteanu: The determination of the concentrations of heavy metals on the Jiu river using IPC- MS, and on the Olt river using AAS. Comparative research, 5-th Conference on Isotopic and Molecular Processes, Cluj – Napoca, 20 – 22 Sept. 2007 (Proceedings to be published in Rev. Chim. 2008).

[7].UNEP GEMS/Water Programme Water Quality Outlook ISBN 95039-11-4 UN GEMS/Water Programme Office; c/o National Water Research Institute, 867 Lakeshore Road, Burlington, Ontario, L7R 4A6 CANADA

[8].Jaakko Mannio, Olli Jarvinen, Riitta Tuominen, Matti Verta: „Survey of trace elements in lake waters of Finnish Lapland using ICP-MS technique”, Sci. tTot. Environ. 160/161 (1995) 433 – 439

[9].Lennart Weltje, Heike Heidenreich, Wangzhao Zhu, Hubert Th. Wolterbeck, Siegfried Korhammer, Jeroen J. M. De Goeij and Bernd Markert: „Lanthanide concentrations in freshwater plants and molluscs, related to those in surface water, pore water and sediment. A case study in Netherland”, Sci. Tot. Environ. 286, Issues 1-3, March 2002, 191 – 214.

[10].Concas, C. Ardau, A. Cristini, P. Yuddas, G. Cao: „Mobility of heavy metals from tailings to stream waters in a mining activity contaminated site”, Chemosphere, 63 (2006) 244 – 253

[11].Zhi-Yong Huang, Qiang Zhang, Jing Chen, Zhi-Xia Zhuang and Xiao-Ru Wang: „Bioaccumulation of metals and induction of metallo-thioneins in selected tissues of common carp(Cyprinus carpio L) co-exposed to cadmium, mercury and lead”, Appl. Organometal. Chem. 21, 101 – 107, 2007

[12].L. Halicy, J. S. Becker, C. Pickhardt, I. Gavireli, A. Burg, A. Nishri, I. T. Platzner: „Characterization of natural water resources in Israel by inductively coupled plasma mass spectrometry”, Internationa Journal of Mass Spectrometry 249 – 250, (2006) 296 – 302

[13].Aoustin E, Schafer A. I, Fane A. G and Waite T. D, Ultrafiltration of natural organic matter, Separation and Purification Technology, 22-23, 63-78, 2001.

[14].Yoon Y, Amy G, Cho J and Her N, Effects of retained natural organic matter (NOM) on NOM rejection and membrane flux decline with nanofiltration and ultrafiltration, Desalination, 173 (3), 209-221, 2005.

[15].Galambos I, Vatai G and Erika Bekassy-Molnar E, Membrane screening for humic substances removal, Desalination, 162, 111-116, 2004.

[16].Qin J-J, Oo M-H and Li Y, Hollow fiber ultrafiltration membranes with enhanced flux for humic acid removal, J of Mem. Sci., 247, 119–125, 2005.

[17].Ravichandran M, Interactions between mercury and dissolved organic matter, A review, Chemosphere, 55, 319-331, 2004.

[18].Goslan H. E, Wilson D, Banks J, Hillis P, Campbell A and Parsons S. A, Natural organic matter fractionation: XAD Resins vs. UF Membranes. An Investigation into THM formation, natural organic matter fractionation: XAD resins versus UF membranes, Wat. Sci and Techn: Water Supply, 4, (5-6), 113-119, 2004.

[19].Toledano M. B, Nieuwenhuijsen M. J, Best N, Whitaker H, Hambly P, de Hoog C, Fawell J, Jarup L and Elliot P, Relation of trihalomethane concentrations in public water supplies to still birth and birth weight in three water regions in England, Environmental Health Perspectives, 113 (2), 225-232, 2005.

[20].Wrobel K, Sadi BBM, Wrobel K, Castillo JR, Caruso JA. Effect of metal ions on the molecular weight distribution of humic substances derived from municipal  compost: Ultrafiltration and SEC with spectrophotometric and ICP-MS detection. Anal. Chem., 2003, 75: 761-767.

General and specific objectives of the project

The main objective of the project is the determination of the mechanism of the penetration of organic and inorganic pollutants at trace level in drinking water.

Specific objectives:

1.  The development of modern methods, of high sensitivity, for the analysis of elements at trace level by inductively coupled plasma mass spectrometry in various matrices: water soil, sediments, vegetal tissues.

2.  The development of methods based on isotope ratio mass spectrometry for the determination of the origin and the dynamics of the surface and underground waters and performing of systematic measurements on the samples collected

3. The development of methods for the measurement of TOC, DOC, and THM by UV spectrophotometry and GC-MS coupling, experimental determinations and the study of the molecular kinetics concerning THM formation.

4.  Building up data bases concerning the concentration and the dynamics of trace elements, DBP and THM in the water destined to the public consumption for the counties Cluj and Salaj and the determination of the mechanism by which heavy metals and THM can reach the drinking water.

Ethical aspects

 The proposed research does not imply experiences on living animals and / or on human subjects. The analytical techniques proposed do not harm the environment, there are no toxic or radioactive emissions and sample collection has no destructive effects. The results of this research aim the improvement of the quality of life, offering information for the diminishing / avoiding the pollution of the drinking water.

The partners will observe the criterions of good practice in research specified in the regulation nr 206/2004. The partners agree that the results of this research: studies, data bases, scientific papers will be a common property of the participants. The analytical methods developed during the evolution of the project will be the exclusive property of those who will have elaborated them.

Detailed description of activities, coherent with the proposed objectives

 Sample collection (water, soil, sediments) is a common activity for all the specified objectives.

Objective 1

▪ A method for sediment and soil samples preparation for the ICP-MS analysis

▪ A method for high turbidity water samples preparation for the ICP-MS analysis

▪ A preparation method for samples of vegetal tissues for ICP-MS analysis

▪ Identification by semi-quantitative methods of the heavy metals and REE present in the investigated matrices.

▪ Development and validation – quantitative methods for the determination of heavy metal and REE concentration in the investigated matrices

▪ The determination of heavy metal and REE concentration on water samples collected monthly from specified locations (surface waters, treatment stations, distribution system, REE in soil sediments vegetal tissues)

Objective 2

▪ Extraction method for the dissolved inorganic and organic carbon (DIC, DOC) in water for the ¹³C isotopic analysis by IRMS

▪ IRMS isotopic analysis of ¹³C ¹⁸O and ²H from the collected waters for the establishment of their origin.

▪ The use of the 19O/16O for the spatial and temporal study of the water accumulations supply

Objective 3

▪ Quantitative methods for the determination of TOC, DOC, and THM by GC, GC-MS and UV spectrophotometry. Method validation.

▪ Sampling and qualitative and quantitative monitoring of TOC, DOC and THM

▪ “In situ” studies concerning DBP formation at the preparation station of Cluj-Napoca

▪ Molecular kinetics studies concerning DBP formation for the drinking waters selected, including the influence of the trace heavy metal on the formation potential of THM.

 Objective 4

▪ Information systematization by the correlation of the results obtained by ICP-MS, IRMS and GC-MS for the determination of the mechanism of penetration of trace level elements and organic pollutants in waters destined to human consumption.

▪ Creation of a data base concerning the concentration of trace elements and REE in water accumulations and the drinking water.

▪ Creation of a data base by data collection regarding water treatment the physico-chemical parameters the raw water disinfection mode and the disinfection by products in Romania

The presumed results of the research are:

▪ the high precision of the analytical methods will allow an evaluation of the masic budget for the elements at trace level and the mechanism of penetration in water of the elements with toxic potential;

▪ methods will be developed for precise isotope ratio determination by IRMS which will permit to establish the supply mechanism of water accumulations;

▪ methods will be developed for precise determinations of TOC, DOC and trihalomethanes (THM) in the water destined to human consumption;

▪ studies of molecular kinetics will be done in order to determine the degree of influencing the formation of THM function of the concentration of the elements at trace level,

▪ a data base will be completed regarding the concentration and the dynamics of heavy metals with high toxic potential (Pb, Cd, As, Hg), useful to the companies preparing and managing the water destined to the human consumption in urban agglomerations from the counties of Cluj and Sălaj.