Water Res. Vol. 17, No. 12, pp. 1815 1821, 1983 Printed in Great Britain
0043-1354/83 $3.00+0.00 Pergamon Press Ltd
SOME ELEMENTS COMPRISING PARTICULATE MATTER D U R I N G SUMMER IN WATERS OF VARIOUS ENVIRONMENTS IN BRITISH COLUMBIA, CANADA SHOZO ISHIZAKA ~, JOHN G. STOCKNER 2, KATSUM1 KOBAYASHI I, KUNIHIRO SHIMA 3, KENJI KATORI 4 a n d HUMITAKE SEKI I
qnstitute of Biological Sciences, University of Tsukuba, Sakuramura, Ibaraki, Japan 305, 2West Vancouver Laboratory, 4160 Marine Drive, West Vancouver, B.C., Canada V7V 1N6, 3Institute of Applied Physics, University of Tsukuba, Sakuramura, Ibaraki, Japan 305 and 4Institute of Physics, University of Tsukuba, Sakuramura, Ibaraki, Japan 305 (Received March 1983)
A~tract--Multi-elemental traces comprising particulate matter in natural water collected during summer in 1978 and 1979 from British Columbia, Canada, were analyzed by or-particle excited X-ray fluorometry. Common elements from all waters examined were Si, C1, Ca and Fe. The similarity of their distribution in different aquatic environments was statistically analyzed. They were distributed homogeneously in the marine environment but heterogeneously in the freshwater environments. No heavy metals concerned with the environmental standards were detected for all waters examined. Key words--multi-elemental traces, particulate matter, British Columbia, or-particle excited X-ray fluorometry, the marine environment, the freshwater environments, the environmental standards
INTRODUCTION In a previous study (Seki et al., 1979), bioaccumulation was shown to be an obvious process to increase metallic elements in the particulate fraction in natural waters. This process must be important for microzonational increase in heavy metal concentrations in various environments such as the terrestrial environment (Day et al., 1975; Laxen and Harrison, 1977; Nightingale, 1975; Revitt and Ellis, 1980; Yamagata and Shigemitsu, 1970), the freshwater environment (Elzerman and Armstrong, 1979; Fjerdingstad et al., 1976; Seki et al., 1979; Waldichuk, 1974; Yamagata and Shigemitsu, 1970) and the marine environment (Abdullah et al., 1972; Goldberg, 1965; Knauer and Martin, 1973; Waldichuk, 1974; Yamagata and Shigemitsu, 1970). "Minamata disease" caused by the human consumption of fishes from Minamata Bay, Japan, contaminated with mercury (Hg) is believed to be one of the most catastrophic examples of the bioaccumulation of heavy metals by marine organisms (The Oceanographical Society of Japan, 1975). This kind of tragedy for human beings was caused by human activities mostly connected with industry. Cadmium (Cd) also causes "Itai-itai disease" through the food chain, primarily starting from the contamination of cadmium by mining activities leading up to the human consumption of bioaccumulated cadmium (The Oceanographical Society of Japan, 1975; Yamagata and Shigemitsu, 1970). In the same ways, almost all the
heavy metals, as well as some other metallic elements are possible objects for bioaccumulation through the food chains eventually leading to human disorders. The necessity of multi-elemental analysis of samples from various environments as reported here are thus important in order to maintain the biosphere in a healthful condition. Most metallic elements of concern in environmental quality are found dissolved in natural waters at concentrations <1 p g l -~ (Waldichuk, 1974). The bioaccumulation of elements with such low concentrations can only be performed with the active transport system in nutrient uptake by organisms (Harold, 1972). Procaryotic microorganisms having a membrane-bound carrier protein are believed to be major agents for this transport system, although many eucaryotic phytoplankters have been recently shown to have similar systems (Hellebust, 1970). These planktonic microorganisms in natural waters can often be responsible for the bioaccumulation of metallic elements as well as for the dynamics of organic solutes in waters. In this report we examine the concentrations of all elements that can be measured qualitatively and quantitatively by an ~-particle excited X-ray fluorometry adjusted especially to measure all metallic elements comprising particulate matter in natural waters of British Columbia, Canada. The concentrations in each environment are also statistically examined to identify the similarity of environments and to relate the accumulation of these elements to
Stamp R i v e r /
Fig. 1. Sampling locations in British Columbia, Canada.
the particulate matter and microbial activities concerned with the dynamics of organic solutes in the waters. DESCRIPTION OF STUDY AREA Great Central Lake is an oligotrophic lake where fertilizer (nitrogen and phosphorus) has been applied for enhancing sockeye salmon populations (Stockner, 1977; LeBrasseur et al., 1978). Kitlope and Meziadin Lakes are slightly glacially turbid, while Lowe and Bonilla Lakes are slightly dystrophic and moderately dystrophic, respectively. Deer Lake is eutrophic. Capilano Lake is an oligotrophic lake, used as a water reservoir for Vancouver City. The Stamp River receives water from Great Central Lake, and joins the Somass River to discharge freshwater into Alberni Inlet. The water in Alberni Inlet off Bamfield is mesooligotrophic, typical for the coastal region of Vancouver Island. The water of the middle part of Alberni Inlet off China Creek is more eutrophic, due to some domestic and industrial discharges from the city of Port Alberni. At the head of Alberni Inlet, the surface water is polluted by dark brown pulpmill effluent. The surface water off Port Mellon in Howe Sound is also polluted by pulpmill effluent. The water of Howe Sound is meso-oligotrophic (Stockner et al., 1977).
MATERIAI..S AND METHODS
Water samples were aseptically collected during summer in 1978 and 1979 in plastic carbuoys from just under the water surface (0.1 m depth) of stations both in the freshwater and marine environments (Fig. 1). Particulate matter in each water sample was collected onto a 0.4#m Nuclepore filter (diameter, 47mm) by filtration of 11. of water immediately after collection. The filtered samples were stored in desiccators until the element analysis commenced. Multi-elemental traces comprising particulate matter in waters were analyzed by an or-particle excited X-ray fluorometry by the scheme illustrated in Fig. 2. This fluorometry apparatus is a modification of the original by Walter et al. (1974). The major modifications are of two types: one is to use a beam of or-particles instead of using a beam of protons as used by Walter et al. (1974), so as to improve the efficiency to excite X-ray emission, and the other is to operate under the condition of flowing helium gas in the target chamber instead of under the vacuum condition as described by Walter et al. (1974), so as to prevent the attenuation of the incident particle beam. Latter modification provides the advantages both of easier sample preparation and quicker sample change. In this apparatus, a series of samples filtered on Nuclepore filters were placed on sample holders. The holders were then inserted into an acrylic chamber through which helium gas flowed. Each sample was set on the central axis of or-beam supplied by Pelletron tandem accelerator. Each emitted fluorescent X-photon from the sample was detected by Si(Li) X-ray detector, turned to an electric pulse with its height proportional to the photon energy [FWHM (full width at half maximum)= 170 eV]. The detected yield and pulse height of every sample have been corrected using those
Elements of particles in waters in British Columbia
Sample Ionb e a m " . ~ Solid state ~ detector / /
Fig. 2. Apparatus of a ~-particle excited X-ray fluorometry. (a) front view of the apparatus; (b) side view of the apparatus; (c) horizontal section at beam part of the apparatus.
of sample standards. These pulses were discriminated and
counted by a multi-channel analyzer. Some characteristic spectra from typical samples from both freshwater and marine environments are shown in Figs 3 and 4. The turnover rates of glutamic acid, glucose and glycollic acid in each water sample were measured microbiologically by the Michaelis-Menten kinetics using each 14C-labelled compound (Seki et al., 1980a, b).
The spectrum of the fluorescent X-rays emitted from each sample of particulate matter in waters of British Columbia shows that metallic elements in particulate matter in these waters were in very 10w concentrations (Figs 3 and 4). Metals of relevance to environmental quality (such as Cd, Cr, Hg and Pb), were all below the detection levels in every sample examined (Tables 1 and 2). Common elements in all water samples examined were Si, CI, Ca and Fe. Mn and Zn were the elements that could be detected quantitatively from sample to sample in the freshwater environment, although they were below the detection level in samples from the marine environment. Potassium could be detected quantitatively for
the samples from most marine environments, and as well from the glacial and eutrophic lakes, whereas it was below the detection level in samples from the oligotrophic and humic lakes and the Stamp River. The turnover times of organic matter suggest that microbial activities associated with such turnover were in the range of steady-state oscillation of each water type (Seki, 1982), as described in the Methods Section. The similarity of water samples was statistically examined based on the concentrations of common elements (Si, C1, Ca and Fe), comprising particulate matter in waters of British Columbia (Table 3). The distributions of these elements were very similar between all stations in the marine environment with correlation coefficients of more than 0.96. The distribution in the marine environment shows good similarity with those of the rivers and the oligotrophic and humic lakes. The distributions were similar also between stations in the fiver and the oligotrophic and dystrophic lakes. Among the lakes examined, similarity was also found between the oligotrophic and humic lakes, the eutrophic and glacial lakes, the eutrophic lake and the reservoir and the eutrophic and humic lakes, respectively. These similarities between stations were analyzed to generalize on the similarity between environments (Table 4). The similarity between the river and marine environment was very high. Although those between the river and lake environment or between the lake and marine environment was not highly recognized, the affinity between the river and lake environment was as expected, greater than between the lake and marine environment. These relations among environments are related directly to the characteristics of water flow i.e. waters of different quality from various lake watersheds flow into the river system to form well mixed water of uniform quality. The river water flows to the marine environment where it mixes to form the brackish surface layer with more uniform quality. High concentrations of particulate silica reflect the presence of diatoms or silicoflagellates in oligo or mesotrophic waters and glacial flower containing silicate minerals in glacial lakes. These high concentrations tended to affect the turnover rate of organic matter in the freshwater environments, notably the turnover rates of glutamic acid and glucose (Table 5). The turnover rate is expressed as reverse of the turnover time, these positive correlations suggest some inhibitory effects of Si and possibly Fe, on the turnover rates of organic matter i.e. inhibitory effects on the microbial activities responsible for the turnover. Iron increased the turnover rates of glutamic acid and glucose in the marine environment (Table 5), but C1 and Ca in particulate matter in water had no statistical effect on the turnover rates of organic matter both in the freshwater and marine environments (Table 5).
S H o z o ISHIZAKA et al.
o i0 z
F i g . 3. X - r a y e m i s s i o n s p e c t r a f r o m s a m p l e s c o l l e c t e d i n t h e f r e s h w a t e r e n v i r o n m e n t , st. L~: G r e a t C e n t r a l L a k e ( u n f e r t i l i z e d ) ; st. R : S t a m p R i v e r ; st. L 3 : K i t l o p e L a k e ; st. L7 : B o n i l l a L a k e ; st. L s : C a p i l a n o L a k e ; st. L s : D e e r L a k e .
Table 1. The elements comprising particles and the turnover time of organic materials in the freshwater environments Concentration (ugl i) Turnover time (h) Sampling location Si CI K Ca Mn Fe Zn Glutamic acid Glucose Glycollic acid Great Central Lake (fertilized) 0.14 2.60 0.08 -0.66 81 45 49 Great Central Lake (unfertilized) 0.12 2.38 -0.20 0.14 0.56 120 170 87 Kitlope Lake 1.35 9.80 LT0 2.55 15.30 390 1800 360 Mediadin Lake 3.00 5.40 7.00 -13.63 -1500 5200 570 Lowe Lake 0.15 5.88 -0.10 -1.83 0.35 690 1000 1600 Bonilla Lake 0.50 8.81 0.13 4.65 -210 150 1300 Deer Lake 1.20 5.90 0.66 0.96 0.12 7.42 5.9 15 30 Capilano Lake 0.14 1.87 -0.24 -1.72 -140 150 230 Stamp River 0.12 2.54 -0.08 0.16 0.56 0.22 97 110 62 Not detected. Detection level (,ugl ~): Si, 0.04; CI, 0.2; K, 0.10; Cd, 0.01; Cr, 0.037; Ca, 0.08; Mn, 0.08; Fe, 0.08; Cu, 0.20; Co, 0.08; Ni, 0.08; Zn, 0.20; Hg, 0.078; Pb, 0.078. Detection level was practically determined as the lowest amount of element that showed clear peak in standard experiments. Table 2. The elements comprisin~ particles and the turnover time of organic materials in the marine environments Sampling location Alberni Inlet off Bamfield Alberni Inlet off China Creek Alberni Inlet at the head Howe Sound Port Mellon Not detected. Detection level is as in Table 1.
Si 0.18 0.06 0.16 0.14 0.10
Concentration (ug l -t) CI K Ca 4.96 0.32 0.28 3.28 0.I0 0.14 2.48 0.10 5.62 0.50 0.34 9.28 0.32 1.16
Fe 0.14 0.36 0.76 0.72 0.60
Glutamic acid 260 11 32 19 24
Turnover time (b) Glucose 240 70 47 110 130
Glycollic acid 560 9.8 150 100 3.7
Elements of particles in waters in British Columbia Ct e.i
I0 5 :
IO 3 O
I0 I 0
I ch =
Fig. 4. X-ray emission spectra from samples collected in the marine environment, st. Mt: Alberni Inlet off Bamfield; st. M2: Alberni Inlet off China Creek; st. M3: Alberni Inlet at the head; st. M4: Howe Sound; st. Ms: Port Mellon.
Table 3. Correlation in the distribution of elements (St, CI, Ca, Fe) comprising particulate matter in water between the sampling station. Each value shows the correlation coefficient (r) M~ 0.88 0.99 0,95 0.27 0.038 0.63 0.96 0.84 0.41 0.99 0.99 0.96 0.99 I R: Stamp River; Ll: Great Central Lake (unfertilized region); lq: Great Central Lake (fertilized region); L3: Kitlope Lake; I-4: Mediadin Lake; Ls: Capilano Lake; Lt: Lowe Lake; LT: Bonilla Lake: Is: Deer Lake; M]: Alberni Inlet off Bamfield; M2: Alberni Inlet off China Creek; M3: Alberni Inlet at the head; M4: Howe Sound; Ms: Port Mellon.
R L~ L2 L~ L4 Ls L6 L7 Ls M~ M2 M3 M4 M~
Li 0.90 1
L2 0.92 0.98 1
L3 0.50 0.47 0.47 1
L4 0AI 0.64 0.20 0.93 1
Ls 0.62 0.76 0.76 0.93 0.73 I
L6 0.91 0,98 0.98 0.57 0.30 0.76 I
L7 0.86 0.91 0.91 0.70 0.48 0.91 0.97 1
Ls 0,46 0.58 0,63 0.99 0.88 0,96 0,69 0,80 1
Mt 0.95 0.99 0.84 0.24 0.062 0.62 0.96 0.84 0.39 1
M2 0.90 0,98 0,96 0.34 0.062 0,69 0.97 0.88 0.48 0.99 1
M3 0.91 0.96 0.97 0.52 0.25 0.81 0.99 0.95 0.64 0.96 0.98 1
M4 0.91 0.99 0.96 0.37 0.080 0.70 0.98 0.89 0.50 0.99 0.99 0.98 1
Table 4. Correlation in the distribution of elements (St, C1, Ca, Fe) comprising particulate matter in water between the lake, river and marine environments. Each value shows the correlation coefficient (r) Lake environment River environment Marine environment Lake environment River environment Marine environment
0.59 0.99 I
SHOZO [SHIZAKAet al. Table5. Correlationbetweenthe turnoverrateof organicmatterand theconcentrationof elements comprisingparticulatematterin eachwaterofthe freshwaterand marineenvironments.Eachvalue shows the correlation coefficient (r) Turnover time of glutamicacid Glucose Glycollicacid Freshwater environment
Si CI Ca Fe Marine environment Si C1 Ca Fe
0.76 0.24 -0.11 0.32
0.85 0.28 0.058 0.70
0.68 -0.027 -0.24 -0.78
0.31 0,37 0.043 -0.72
DISCUSSION The analytical method using or-particle excited X-ray fluorometry has an advantage when measuring multi-elemental traces from particulate matter in natural waters with satisfactory detection levels for certain constituents for environmental studies. (The various detection levels for some elements are shown as a footnote in Table 1.) Concentrations of all these elements can be measured simultaneously for each sample by the s-particle irradiation method. N o heavy metals of concern in aquatic environmental quality (Waldichuk, 1974) were present in significant concentrations in water examined from British Columbia. Iron was found as the only c o m m o n metal in particulate matter in all waters on dates examined. The concentrations of Fe, however, were generally still low. In glacially oligotrophic lakes, the concentration of Fe was the highest and in the stagnant deep oligotrophic lake, Great Central Lake, as well as in the Stamp River that receives water from the lake, it was t h e lowest. M n and Zn were the next most c o m m o n metals in particulate matter in most samples. As these metals could not be detected in many waters examined, their concentrations were very low even for the samples where quantitative measurement was possible. All the metal concentrations of particulate matter in waters of British Columbia were one or two orders of magnitude lower than in samples from irrigation waters of Japan (Seki et al., 1979). Iron is required by all organisms as a micronutrient, because it is essential for oxidationreduction reactions in their metabolism. However, our results suggest that Fe may have an inhibitory effect on microbial metabolism as reflected by the turnover rate of certain organic substances in the freshwater environment of British Columbia. This is in contrast with what was observed in the marine environment of British Columbia (Alberni Inlet), where Fe appeared to have a favourable effect on microbial activities. The possible reason for these differences may be related to concentration i.e. the concentrations were from 0.5 to 1 5 . 0 # g l -t in the freshwater environment, whereas they were consistently < 1 # g l -~ in the marine environment. Therefore, perhaps 1.0 p g I ~may be the threshold value of particulate Fe in natural waters for this element to
- 0.0085 0.54 -0.17 0.019 0.65 -0.13 -0.38 -0.58
have favourable or inhibitory effect on microbial activities, especially in the inland waters such as glacial lakes where a great part of the bacterial flora exists growing on particles in the water (e.g. Rheinheimer, 1980). The metabolism of these microorganisms are promoted by the favourable effect of solid surfaces of particles (e.g. ZoBell, 1972; Seki, 1982). Other factors such as chelation must be also important, but were not considered in this study.
Acknowledgements--The authors wish to thank Dr M. Waldichuk for valuable comments, and K. S. Shortreed, E. A. MacIsaac, R. Carr, A. Page and M. Sato for technical assistance. This work was funded by the Lake Enrichment Program of Federal-Provincial Salmonid Enhancement Program of Canada and the Nuclear and Solid State Research Project of the University of Tsukuba.
Abdullah M. I., Royle L. G. and Morris A. W. (1972) Heavy metal concentration in coastal waters. Nature 235, 158-160. Day J. P., Hart M. and Robinson M. S. (1975) Lead in urban street dust. Nature 235, 343-345. Duce R. A., Quinn J. G., Olney C. E., Potrowitcz S. R., Ray B. J. and Wade T. L. (1972) Enrichment of heavy metals and organic compounds in the surface microlayer of Narragansett Bay, Rhode Island. Science 176, 161-163. Elzerman A. W. and Armstrong D. E. (1979) Enrichment of Zn, Cd, Pb and Cu in the surface microlayer of Lake Michigan, Ontario and Mendota. Limnol. Oceanogr. 24, 133-144. Fjerdingstad E., Fjerdingstad E. and Popea F. (1976) Analysis of heavy metals and bacteria in sediments from Danish lignite pits. Arch. Hydrobiol. 77, 226-253. Goldberg E. D. (1965) Minor elements in sea water. In Chemical Oceanography (Edited by Riley J. P. and Skirrow G.), pp. 163-196. Academic Press, New York. Harold F. M. (1972) Conservation and transformation of energy by bacterial membrane. Bact. Rev. 36, 172-230. Hellebust J. A. (1970) The uptake and utilization of organic substances by marine phytoplankters. In Organic Matter in Natural Waters (Edited by Hood D. W.), pp. 225-256. University of Alaska. Knauer G. A. and Martin J. H. (1973) Seasonal variations of cadmium, copper, manganese, lead and zinc in water and phytoplankton in Monterey Bay, California. Limnol. Oceanogr. 18, 597-604. Laxen D. P. H. and Harrison R. M. (1977) The highway as a source of water pollution. Water Res. 11, 1-11. Lebrasseur R. J., McAllister C. D., Barraclough W. E., Kennedy O. D., Manzer J., Robinson D. and Stephens K.
Elements of particles in waters in British Columbia (1978) Enhancement of sockeye salmon (Oncorhynchus nerka) by lake fertilization in Great Central Lake: summary report. J. Fish. Res. Bd Can. 35, 1580-1596. Nightingale H. J. (1975) Lead, zinc and copper in soil of urban storm runoff retention basins. J. Am. Wat. Wks Ass. 67, 443~t46. Revitt D. M. and Ellis J. B. (1980) Rain water leachates of heavy metals in road surface sediments. Water Res. 14, 1403-1407. Rheinheimer G. (1980) Aquatic Microbiology, 2rid Edition, 235 pp. Wiley, Chichester. Seki H. (1982) Dynamics of Organic Materials in Aquatic Ecosystems, 201 pp. CRC Press, Inc., FL. Seki H., Maclsaac E. A. and Stockner J. G. (1980a) The turnover rate of dissolved organic material in waters used by anadromous Pacific salmon on their return to Great Central Lake on Vancouver Island, British Columbia, Canada. Arch. Hydrobiol. 88, 58-72. Seki H., Shortreed K. S. and Stockner J. G. (1980b) Turnover rate of dissolved organic materials in glaciallyoligotrophic and dystrophic lakes in British Columbia, Canada. Arch. hydrobiol. 90, 210-216. Seki H., Takahashi M., Kobayashi K. and Ishizaka S. (1979) Particulate metals in waters of a typical irrigation river: The River Sakuragawa, Japan. Water, Air, Soil Pollut. 12, 265-271.
Stockner J. G. (1977) Lake fertilization as a means of enhancing sockeye salmon populations: the state of the art in the Pacific Northwest. Fish. Mar. Serv. Technol. Rept. 740, 1-14. Stockner J. G., Cliff D. D. and Buchanan D. B. (1977) Phytoplankton production and distribution in Howe Sound, British Columbia: a coastal marine embaymentfjord under stress. J. Fish. Res. Bd Can. 34, 907-917. The Oceanographical Society of Japan (1975) The present status of investigations related to pollution in the marine environment. Special number October 1975. J. Oceanog. Soc. Jap. 1-244 (in Japanese). Waldichuk M. (1974) Some biological concerns in heavy metals pollution. In Pollution and Physiology of Marine Organisms (Edited by Vernberg F. J. and Vernberg W. B.), pp. 1-57. Academic Press, New York. Walter R. L., Willis R. D., Gutknecht W. F. and Joyce J. M. (1974) Analysis of biological, clinical and environmental samples using proton-induced X-ray emission. Anal. Chem. 46, 843-855. Yamagata N. and Shigemitsu I. (1970) Cadmium pollution in perspective. Bull. Inst. Publ. Hlth 19, 1-27. ZoBell C. E. (1972) Substratum 7.1 bacteria, fungi and blue-green algae. In Marine Ecology (Edited by Kinne O.), pp. 1251-1270. Wiley-Interscience, London.