A large number of these residues are identified and categorized as environmental toxins each year. Scattering and bio-accumulation of rare earth elements REEs in the aquatic environment in southern China have resulted from increased industrial and agricultural applications. High REE concentrations in the substrate water in which water hyacinth grew could possibly enter the human food chain and lead to adverse public health problems.
A large number of these residues are identified and categorized as environmental toxins each year. Scattering and bio-accumulation of rare earth elements REEs in the aquatic environment in southern China have resulted from increased industrial and agricultural applications. High REE concentrations in the substrate water in which water hyacinth grew could possibly enter the human food chain and lead to adverse public health problems.
A large number of these residues are identified and categorized as environmental toxins each year. Scattering and bio-accumulation of rare earth elements REEs in the aquatic environment in southern China have resulted from increased industrial and agricultural applications. High REE concentrations in the substrate water in which water hyacinth grew could possibly enter the human food chain and lead to adverse public health problems.
The Science of the Total Environment 214 1998 7985
Bio-accumulation of environmental residues of rare earth . elements in aquatic ora Eichhornia crassipes Mart. Solms in Guangdong Province of China H. Chua U Department of Ciil and Structural Engineering, The Hong Kong Polytechnic Uniersity, Hung Hom, Hong Kong Abstract . Scattering and bio-accumulation of rare earth elements REEs , including the inner transition series, in the aquatic environment in southern China have resulted from increased industrial and agricultural applications. Environmental residues of REEs entered into aquatic ora, namely Eichhornia crassipes, commonly known as water hyacinth, via the root system in contaminated substrate water and could distribute to various parts of the plant. REEs could also bio-accumulate and concentrate in the leaves at a concentration ratio of approx. 3 times regardless of initial REE concentration in the substrate water. REEs could also enter into the plant via the leaves that are exposed to atmospheric contaminants. While ofcially permitted residual concentrations of mixed REE nitrates in foodstuffs or animal feedstocks are not available, high REE concentrations in the substrate water in which water hyacinth grew could possibly enter the human food chain and lead to adverse public health problems. 1998 Elsevier Science B.V. Keywords: Bio-accumulation; Environmental residue; Rare earth elements; Water hyacinth 1. Introduction Applications of chemical substances containing metals in the industry, agriculture and different U Tel.: q852 27666072; fax: q852 23346389. areas of human activities have led to scattering and bio-accumulation of metal residues in the
environment Denchev, 1994; Chua et al., 1995;
. Chua and Hua, 1996 . A large number of these residues are identied and categorized as envi- ronmental toxins each year. In particular, scatter- ing of REEs is known to lead to severe changes of elemental balance in the environment and the 0048-9697r98r$19.00 1998 Elsevier Science B.V. All rights reserved. . PI I S0 0 4 8 - 9 6 9 7 9 8 0 0 0 5 5 - 2 ( ) H. Chua rThe Science of the Total Enironment 214 1998 7985 80 biosphere, which in turn, have the potential to . endanger public health Kuang et al., 1992 . Rare earth elements include three Group IIIA . . . elements, namely Sc 21 , Y 39 and La 57 , and the inner transition series, namely the lan- . . thanides from Ce 58 to Lu 71 . These elements are transitional in the atomic state and are pre- sent in many of their compounds as tripositive
ions which have a noble gas conguration Bell
. and Lott, 1972 . Solutions of the tripositive ions are distinctly coloured. They share similar physico-chemical properties but are generally different from the common transitional metals. The more commonly used REEs are Ce, La, Pr, Nd, Sm and Y. Recent widespread applications of REEs in agricultural activities include forestry, animal husbandry and aquaculture. REEs are contained in bactericides, microelement fertilizers . and animal feeds Sun et al., 1994 . The main element-pollutants in phosphogypsum used in agriculture are uorine, sulphur, strontium and the REEs. There is a tendency for strontium and the REEs to scatter or accumulate in soil and the . water environment Gorbunov et al., 1992 . High concentrations of REEs have been detected in plants, which were related to the presence of REE traces in the soils on which the plants grow and were taken up by the roots and transported
to various parts of the plants Kuang and Liu,
. 1981; Ichihashi et al., 1992; Kuang et al., 1992 . The capacity of plants or agricultural crops to accumulate REEs depends on the plants species and the REE contents in the substrate soils or . rocks Volokh et al., 1990; Ichihashi et al., 1992 . Beet and apple, in particular, were among the major biological stores of REEs. Conventionally, REEs are extracted from high-grade ores, such as thortveitite, gadolinite, xenotime, yttrotantalite, samarskite and fergu-
sonite, by electrolysis of fused chlorides Bell and
. Lott, 1972 . In the process of concentration of ores, extraction of crude metals and nal rening by ion-exchange chromatography, scattering of REEs in the water and atmospheric environments as residues may occur. More recently, REEs are used as ne chemicals in modern industries . Ichihashi et al., 1992 . Atmospheric airborne wa- ter droplets and particles bearing REEs origi- nated mainly from oil-red power stations and transportation vehicles using REEs as catalysts . Olmez et al., 1991; Huang et al., 1994 . These REEs, while in contact with plants, may be absor- bed mainly via the leaves. Gabriel and Patten . 1995 considered the level of accumulation of lanthanum, cerium and samarium in mesquite leaves an important indicator for the level of urban water and atmospheric pollution. The REEs absorbed into plants, either via the roots or leaves, could be distributed to and bio-accumulate in various parts of the plant. The REEs enter the human body mainly via ingestion of contaminated food and inhalation of airborne dust particles bearing REEs. While REEs taken into the human body are mostly excreted, a small amount may enter the blood stream through ion exchange and can be de-
posited in various organs Koeberl and Bayer,
. 1992 . It has been predicted that the industrial and agricultural usage of REEs and the resulting environmental contamination by REEs will grow
rapidly in the next few decades Volokh et al.,
. 1990 . Prolonged occupational, environmental and dietary exposure to REEs may adversely affect human health. A number of diseases have pre- liminarily been associated with exposure to REEs . Sabbioni et al., 1982; Ding and Ma, 1984 . How- ever, published data on the effects of REEs on the environment and the biosphere are limited, primarily due to the lack of sensitive analytical technique to estimate the trace levels of these elements in air, water, soil, sediment and biologi- . cal samples Markert, 1987; Markert et al., 1989 . Consequently, REEs are usually not included in the wastewater quality standards for discharge
into surface waters and foul sewers Hong Kong
. Environmental Protection Department, 1991 . Also, little is known of the mechanisms by which REEs accumulate in and affect the biosphere, particularly aquatic ora and agricultural crops that form a substantial part of the human food chain. This article describes a study on the accumula- tion and distribution of REEs in Eichhornia cras- sipes, commonly known as water hyacinth, in simulated cases of exposure of roots to substrate water contaminated with REEs and exposure of ( ) H. Chua rThe Science of the Total Enironment 214 1998 7985 81 leaves to atmospheric particles bearing REEs. Water hyacinth was used in this study because it is an important aquatic ora of the inland water courses in Southern China. Water hyacinth is frequently used as a piggery feedstock and hence enters the human food chain. 2. Materials and methods 2.1. Aquatic ora species and culture solution w Samples of water hyacinth Eichhornia crassipes . x Mart. Solms were harvested from inland water courses in the Guangdong Province of Southern China. Only plants with 12 full-grown leaves and a root system of approx. 60 cm in overall length were selected. Each plant sample was cultured in a vessel containing 10 l of culture solution. The formulation of the culture solution was in accor- dance with the standard hydroponic medium de- . scribed by Hao 1994 . 2.2. Simulation of substrate water contamination by REE Solutions of micro-element fertilizer containing nitrates of REEs were prepared at 100, 300, 600, 900, 1200 and 1500 ppm. The micro-element fer- tilizer, containing 38.70 wt.% of REE O , was 2 3 supplied by the Henan Shangqiu Chemical Engi- neering Company. A 40-ml aliquot of each solu- tion of microelement fertilizer was added into the 10-l culture solution of each plant sample. De- ionised water was similarly added to one sample to act as the control. After 21 days, plant samples were harvested and washed with distilled water. Each plant sam- ple was divided into three parts, namely roots, stems and leaves. These parts were boiled in 4 N HCl solution to extract the bio-accumulated REE. The extracts were analyzed for REE with an inductively coupled plasma-atomic emission spec- . . troscope ICP-AES Shimatsu Type Q1012 . The ICP-AES preparation and analytical methods were in accordance with that described by Guo . . 1984 and Chao 1985 . The total content of REEs, including Ce, La, Pr, Nd, Sm and Y, were . determined and expressed as mgrg dry wt. of . each part of the plant ppm . 2.3. Simulation of atmospheric exposure to REE 141 . Ce NO was used as the radioactive iso- 3 3 tope tracer to determine the absorption of the REE by water hyacinth leaves that were exposed to atmospheric particles bearing the REE com- pound. The distribution and bio-accumulation of the REE in different parts of the plant was also determined. A 0.0215 mCi of 300 ppm 141 . Ce NO solution specic radioactivity of 1.25 3 3 . mCirml was evenly smeared on all the 12 leaves of the plant sample in order to simulate the exposure of leaves to the REEs that were in contact with the leaf surface. This procedure was 141 . repeated four times. Ce NO solution used in 3 3 this procedure was prepared by reacting nitric acid with 141 CeO provided by the Chinese Insti- 2 tute of Nuclear Energy. Samples of the plants were collected after 1, 2, 4, 8, 12 and 16 days. The samples were washed . with Ce NO carrier solution followed by dis- 3 3 tilled water. The different parts of the plant, namely roots, stems and leaves, were separately oven dried, machine ground and weighed. The relative radioactivity in the processed samples of each part of the plant was determined using an alpha-beta-gamma low background automatic . counter Baird Corporation . All data were cor- rected for decay and statistically treated. 3. Results and discussion 3.1. Uptake and bio-accumulation ia root system The uptake and distribution of REEs via the water hyacinth root system from the substrate water added with solutions of micro-element fer- tilizer containing nitrates of REEs are sum- marised in Table 1. This concentration range of 1001500 ppm of REE nitrates is typical in mi- cro-element fertilizer solutions used in this re- gion. For instance, the common dosage of REEs in agricultural plantations in China is ofcially . led as 300 ppm Kuang et al., 1992 . The corre- ( ) H. Chua rThe Science of the Total Enironment 214 1998 7985 82 Table 1 Accumulation of REEs in water hyacinth Concentration of Concentation of Bio-accumulated Concentration c nitrates of REEs nitrates of REEs REEs in ppm ratios in fertilizer in culture b Root Stem Leaf Root Stem Leaf a . . solution ppm solution ppm 100 0.4 3.51 4.19 5.57 8.8 10.3 13.9 300 1.2 3.48 5.42 7.65 2.9 4.5 6.4 600 2.4 4.97 7.30 10.50 2.1 3.0 4.4 900 3.6 5.62 9.65 12.44 1.6 2.7 3.5 1200 4.8 6.65 12.19 14.12 1.4 2.5 2.9 1500 6.0 7.56 13.79 16.27 1.3 2.3 2.7 a REE concentrations in culture solutions were calculated based on the amount of REEs applied in 10 l of culture solution. b The bio-accumulated values are averages of three samples. c REEs in different partsrREEs in culture solution. sponding REE concentrations in the culture solu- tions were calculated based on the amount of REEs applied in 10 l of culture solution for each plant sample. Results in Table 1 show that with this concentration of 300 ppm in the fertilizer solution, corresponding to 1.2 ppm in the subs- trate water, water hyacinth was able to accumu- late up to 3.48, 5.42 and 7.65 ppm of REEs in the roots, stems and leaves, respectively. Bio-accumu- lation of REEs in the various parts of the plant sample with all the different concentrations in the substrate water tested was in the order of leaves, stems and roots, in terms of relative abundance. The bio-accumulated REE values in Table 1 are averages of three samples. These observations were similar to those reported by Kuang and Liu . . 1981 and Kuang et al. 1992 from similar stud- ies carried out with other agricultural crops, such as rice and sugarcane. Using fertilizer solutions within the concentra-
tion range tested, namely 1001500 ppm equiv-
. alent to 115 mg of nitrates of REEs , the REE bio-accumulation in roots, stems and leaves in- creased with increasing REE concentration in the substrate water. The correlation between concen- trations of REE residues in the various parts of the plant sample and that in the substrate water . appeared relatively linear Fig. 1 . If the REE Fig. 1. Bio-accumulation of REEs at different substrate concentrations. ( ) H. Chua rThe Science of the Total Enironment 214 1998 7985 83 residual concentrations in the various parts was represented by Y and the REE concentrations in substrate water was represented by X, then the correlations could be expressed as follows. For the roots, Ys1.94q0.03X, r s0.999, r 0.055. s0.755 and r s0.875. For the stems, Ys 0.015. 2.39q0.01X, r s0.999, r s0.755 and r 0.055. 0.015. s0.875. For the leaves, Ys4.00q0.01X, r s 0.992, r s0.755 and r s0.875. 0.055. 0.015. Fig. 2 shows the concentration ratio of the bio-accumulated REE concentrations in the vari- ous parts to the REE concentration in the subs- trate water with different REE concentrations in the substrate water. The concentration ratios were calculated by dividing the bio-accumulated REEs in different parts of the plant by the REE con- centrations in the culture solutions. When the REE concentration in the substrate water was 0.4 ppm, water hyacinth was able to bio-accumulate REEs to concentrations above 8.8 times the REE concentration in the substrate water. In particu- lar, the leaves were able to bio-accumulate REEs up to a concentration ratio of 13.9. These concen- tration ratios decreased almost exponentially with increasing REE concentrations in the substrate water. However, as the REE concentration in the fertilizer solution was increased above 900 ppm, resulting in more than 3.6 ppm of REEs in the substrate water, the REE concentration ratio in various parts approached constant values between 1.5 and 3.0. These results showed that water hyacinth could bio-accumulate REEs to concen- tration ratios higher than that in other agricul-
tural crops, namely rice and sugarcane Kuang
. and Liu, 1981; Kuang et al., 1992 . 3.2. Uptake and bio-accumulation ia leaes The absorption and distribution of 141 Ce tracer in water hyacinth are summarized in Table 2. The results show that Ce could be absorbed, via the stoma and cuticle on the surface of the leaves. After absorption via the exposed leaves, Ce was rapidly distributed to various parts of the plant. The bio-accumulation of Ce in the roots, stems and leaves accounted for 12.7, 41.1 and 46.1%, respectively, of that in the entire plant after 1 day of observation. This percentage distribution re- mained relatively constant throughout the 16-day observation. Bio-accumulation of Ce in the leaves accounted for approx. 50% of that in the entire plant. Bio-accumulation in various parts of water hyacinth was in the order of leaves, stems and roots, in terms of relative abundance. This order Fig. 2. Concentration ratio of REEs. ( ) H. Chua rThe Science of the Total Enironment 214 1998 7985 84 Table 2 Bio-accumulation of cerium via leaves and distribution in different parts Parts Day 1 2 4 8 12 16 a . Roots Accumulation cpm 1089 1341 2087 2270 2069 1999 b . Percentage % 12.7 14.2 12.8 10.4 13.2 13.5 . Stems Accumulation cpm 3515 3987 5590 7715 5211 4989 . Percentage % 41.1 42.1 34.3 35.4 33.3 33.7 . Leaves Accumulation cpm 3945 4138 8611 11 821 8348 7816 . Percentage % 46.1 43.7 52.9 54.2 53.4 52.8 . Entire Accumulation cpm 8549 9466 16 288 21 806 15 628 14 804 c . plant Percentage % 0.87 0.96 1.65 2.21 1.59 1.50 a Figures are averages of four plant samples. b Ce in each plant as a percentage of that in the entire plant. c . Percentages bio-absorption of Ce in entire plantrCe applied on leaf surface =100. Quantity of Ce applied was taken as 985=10 3 cpmrplant. was consistent with that observed previously when the root system of the plant samples were ex- posed to REE. This observation was also consis-
tent with our previous studies on rice Kuang and
. . Liu, 1981 and wheat Zhu et al., 1987 . The bio-accumulation of the radioactive ele- ment in the various parts reached a highest level on the eighth day and then gradually decreased to . constant levels Fig. 3 . Absorption of Ce in the leaves reached a highest level of 11 821 cpm, accounting for 54.2% of that in the entire plant. The absorption and distribution of Ce in the entire plant was equivalent to 0.872.21%, in terms of radioactivity, of the total amount of 985=10 3 cpm applied on the leaves initially. 4. Conclusion REEs could enter into water hyacinth via the root system in substrate water that was contami- nated by REEs and via the leaves that were exposed to atmospheric contaminants. In either Fig. 3. Bio-accumulation of REEs via leaves. ( ) H. Chua rThe Science of the Total Enironment 214 1998 7985 85 case, the absorbed REEs could be distributed to and bio-accumulate in various parts of the plant. 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