Environment
Protection
Vol. 32
Engineering No. 2
2006
ANDRZEJ K.M. KABZIŃSKI*.#. HELENA GRABOWSKA**. JERZY CYRAN**. RENATA JUSZCZAK". ALICJA ZA WADZKA DOMINIK E. SZCZUKOCKI*. KONRAD SZCZYTOWSKI*
*"*,
OZONATION-BASED REMOVAL OF MICROCYSTIN FROM DRINKING WATER DRA WN FROM THE ARTIFICIAL LAKE OF SULEJÓW, POLAND
Cyanobacteria can produce toxins and are also responsible for the taste and odour of water, which significantly impairs its quality. Removal of cyanobacterial cells with their intracellułar compounds during water treatrnent not onły improves the taste and odour of the treated water, hut also reduces the concentration of toxic metabolites. In the present study, the ozonarion of water in prctreatment plant near Sulejów artificial lake was tested, The concentrations of MCYST-LR and other isoforms of this hepatotoxin were determined at different steps ar the pretreatrnent proces s by SPE and RP-HPLC methods.
1. INTRODUCTION Recognition of the toxicity of cyanobacterial blooms and scums can be traced in the literature over at least the past 140 years [l], [2]. Initial associations of cyanobacterial blooms and scums with wild and domestic animaI poisoning episodes and human health problem in several countries raised the possibility of producing toxins by the common bloom-forming cyanobacteria. Large-scale toxicity assessment surveys have subsequentIy been performed on cyanobacteriaI bIoom and scum sampies from manycountries (table 1) [3].
ar
* University of Łódź, Faculty Physics and Chernistry, Department of Generał and Inorganic Chernistry, Environmental and Biorncdical Analysis Laboratory, 90-136 Łódź, 68 Narutowicza Str., Poland. ** Watcr Supply and Sewage Works of Łódź. 90-133 Łódź. 52 Wierzbowa Str., Poland. *** Technical University ofŁódź. Department ot" Environmental and Processing Engineering. 90-924 Łódź. 213 Wólczańska Str .. Poland. # Corresponding author: tel.: (48-42) 635-57-92. fax.: (48-42) 678-39-58, c-mail:
[email protected] or
[email protected]
18
A.K.M.
KABZIŃSKl et al.
Table Toxic cyanobacterial
Europc
Americas Middle East and Asia Africa
Australasia Marinę
l
blooms in water [3 J
Belgiurn. Czech Rcpublic, Denmark, Finland. France, Germany, Greecc, Hungary. lrcland. !taly. The Netherlands, Norway, Poland, Portugal. Russiu, Slovakia, Sweden. Switzerland, Ukraino, United Kingdom Aracntina, Bcrrnuda, Brazil, Canada, Chile, U.S.A., Vcnezuela lndia, Israel, Japan, Malaysia, Peoples Republic of China, Bangladcsh. Saudi Arabia, South Korea, Thailand Eavpt, Ethiopia, Morocco, South Africa, Zimbabwe Australia, New Calcdonia, New Zenland Atlantic Ocean.Baltic Sca. Caribbean Sca, Indian Ocean
Table Properties Toxins
of cyanobacterial
Sources
Nodularin
Nodularia
Microcystin
Microcystis, /viabaena. Nostoc. Oscillaioria Cylindrospcr-mopsis, Umezaki
Cylindrosperrnopsin Anatoxin-a
Anatoxin-a(s)
Anabaena, Microcystis. Oscillatoria. Phortnidium. Aohonizomcnon Anabacna
Homoanatoxi n-a (saxitoxin, neosaxiioxin)
Phonnidiutn. Aphauizomeuon, Anabaena
LPS
Microcystts. Oscillatoria
2
toxins [3], [63J, [64J
Molecular structurc HEPATOTOXINS cyelie pentapeptide cyclic heptapeptide
cyclie guanidine alkaloid NEUROTOXINS sccondary amine alkaloid
guanidinum methyl phosphate ester alkaloids
Number ot' variants >6 >70
l
Modes of action hepatotoxic, tumour orornoters, PPase inhibitor hepatotoxic. tumour promoters, PPase inhibitor
hepatotoxic.
tumour
I promoters l
ncurotoxic. depolarizing neuromuscular blocker
I
ncurotoxic, cholinoesterase inhibitor
8
neurotoxie, blocker
sodium channet
ENDOTOXiNS
upopotysaccnarides
>3
toxic shock, gastroenteritis,
inflamation
Increased nutrient levels or eutrophication of natural waters can cause massive blooms of cyanobacteria. Since toxin-producing species often predominate in thick
Ozonation-based
retnoval of microcystin [roin drinking water
19
surface blooms, it can be assumed that they pose potential health risk also to humans through the household and recreational use of water. In some cases, cyanobacteria may contaminatethe sources of raw water and their toxins can be found in potable water. Several incidents of human illness have been attributed to the cyanobacteria present in drinking water, although, in generał, algal toxins have not been responsible for these incidents [4]-[7], since only one such case was clearly associated with MCYSTs [7]. Some important genera found in eutrophic waters all over the world in the form of algal bloom are as follows: Anabaena, Aphanizomenon, Cylindrospermopsis, Fischerella. Gloeostrichia, Gomphosphaeria, Hapalosiplion, Lyngbya, Microcystis, Nodularia, Nostoc, Oscillatoria. Pseudoanabaena, Schizothrix. Scytonenia and Umezaki [3]. Cyanobacteria may produce acute toxins such as hepatotoxic oligopeptides (microcystins, nodularins and cylindrospermopsis) and neurotoxic alkaloids (anatoxin-a, anatoxin-a(s), homoanatoxin and aphanatoxin) (table 2). Nodularin, microcystins and microcystin-LR (MCYST -LR) are the members of a large family of MCYST analogues produced by cyanobacteria and are known to inhibit protein phosphatases l and 2A [8]-[ 10]. This may result in the formation of tumors in experirnentul animals [11]-[13]. Cyanobacterial hepatotoxins have recently received attention following the report by JOCHIMSENet al. [14], who described the death of 50 patients subjected to dialysis treatment with MCYST-LR-contaminated water. The efficiency of the treatment process of drinking water contaminated with the microcystin toxins has some health implications recently reviewed by LAMBERTet al. [15]. Many strategies of the removal of cyanobacterial toxins from water have been investigated. Conventional water treatment (coagulation/sedimentation and filtration) have been reported to be ineffective in removing MCYSTs [16J-[19]. Water treatment studies condueted (laboratory and pilot-plant scales) have shown that granular activated carbon (GAC) filtration is effective in removing cyanobacterial toxins from drinking water [ 17], [19]-[22]. Powdered activated carbon (PAC) removes MCYST but its doses should be higher than those generaIly used in water treatment [16], [17], [19], [20], [22]. NICHOLSONet al. [23], [24] have reported that MCYST -LR and nodularin can be removed from water by its ehlorination, but unfortunately chlorination of organie compounds can also cause adverse health effects in humans. Also ferric chloride can be used to decompose MCYST in water. The iron(III) ehloride decomposes MCYST into (2S,3S,8S)-3-amino-2,6,8-trimethyl-1 0-phenyldeca-4E,6E-dienoic acid [25]-[27]. ROSITANOet al. [28], [29] have observed that ozone treatment allows the MCYST-LR and nodularin coneentration to be reduced below the detection limits. Several studies have shown that the toxin removal is strongly dependent on the dose of ozone [30]-[35]. There is also some evidence mar rhe effecriveness of ozonarion depends on water quality [28], [30J, [32], [34]. However, it has also been found that destruction of hepatotoxins is pH-dependent, and in the medium of alkalinę reaction (pH 7.3-9.9) usually experienced during algal bloom is less effecti ve. Photocatalysis in the presenee of TiO~ is eonsidered to be a very efficient method of MCYST -LR destruction.
20
KABZIŃSKI et al.
A.K.M.
In Poland, the presence of cyanobacterial toxins has been monitored since 1993, mainly in Sulejów, Jeziorsko and Włocławek reservoirs of municipal drinking water (central Poland) (tabIes 3 and 4). As in other countries MCYST-LR is the main fraction of toxins [37]-[39]. Table
3
The concentrations of MCYST-LR in algal sampIes and water from Sulejów artificiallake [37]-[39], [65] Mean eontent of MCYST-LR Year
1993 1994 1995 1996 1997 1998 1999 2000 2001
Algal sample [ug/g]
Water [ug/drrr']
Range
Mean
Range
Mean
16-149
74 +/- 56 81 +/-71 120 +/- 111 99 +/- 67 103 +/-86
x x 0.0-6.8 0.0...5.3
x x 2.3 +/- 1.8 1.9 +/- 1.2 1.5 +/- 1.4
5-191 8-427 6-227 7-286 4-168 5-469 6-395 3-196
76 136 124 84
+/- 53 +/- 124 +/- 120 +/-79
0.0-4.6 0.0...2.7 0.0...5.1 0.0...6.3 0.0...2.5
0.8 +/-0.7 2.4 +/- 2.1 2.3 +/- 1.9 0.7 +/-0.6
SampIes were collected from May to November. x - no data.
Table
4
The concentrations of MCYST-LR in algal sampIes from Jeziorsko and Włocławek artificiallakes in 1996-2001 [37]-[39], [65] Content of MCYST-LR in bloom sampIes [ug/g] Year
Jeziorsko Artificial Lake Range
Mean
Rangę
Mean
1996
15-390 18-450 10...275
187 +/-115
8-460
212 +/- 101 93 +/- 102 229 +/- 112 187 +/- 136 115 +/~89
12-438 6-283 9-489
210+/-135 206 +/- 112 84 +/- 100 235 +/- 157 191 142 108 +/- 91
1997 1998 1999 2000 2001
11-478 8-3537-287
WIocląwek Artificial Lake
7-372 9-315
+/-
SampIes were collected from May to Novernber.
This paper presents the results obtained in water treatment plant near the Sulejów reservoir. Examinations were carried out in 199_8-2001 at different concentrations of ozon e and chloride oxide.
Ozonation-based removal of microcystinfrom drinking water
21
2. MATERIALS AND METHODS
2.1. OZONATION OF TREATED WATER
Water was collected from Sulejów reservoir in Bronisławów from 1.0 m over the bottom. lnan initial purification step, CIOz disinfection was applied. Then the water was delivered to Water Treatment Plant in Kalinko whose distance from the reservoir was some 36.6 km. The water transported is: (a) alkalized by hydrated lime, (b) filtered through powdered activated carbon, (c) coagulated and clarified on suspended sediments, (d) alkalized by milk of Iime and sodium Iye, (e) filtered through sand or sand-anthracite filter, (f) chemically oxidized by ozone (03) and finally (g) disinfected by Cl02 or Clz. After treatment process water is sent (at the distance of about 7.7 km) to Łódź-Chojny pumping station from where it is delivered to consumers. Presently a daily water requirement ranges from ca. 30x103 to 50x103 rn'. Water treatment and its de1ivery from Bronisławów (sieve chamber) to Łódź-Chojny (reservoir and pumping station) last for 2.0-3.5 days. The doses of CI02 and 03 were changed, depending on the quality of water iri the Sulejów reservoir, being higher in the case of floods or cyanobacterial blooms. The doses of Cl02 ranged between 2.0 and 2.5 glm3, and the doses of ozone ranged between O and 4.0 g OJm3 of water. Coagulation was of an essential importance in removing cyanobacterial and algal biomass from water.
2.2. SAMPLES AND MATERIALS
Water sampIes were collected from Sulejów reservoir (artificial lake), Kalinko station and Łódź-Chojny from June to November in the years 1998-2001. The samples were collected from the depth of 0.3-0.6 m, poured into dark glass bottles, then to each of them sodium azide (NaN3) (0.05% w/v) was added. The bottJes were kept at +4 "C. Water was also collected from sieve chamber. 1.0 m over the bottom of artificial lake, and its preparation wassimilar to that of surface water. The standards of such microcystins as MCYST -LR, MCYST -RR, MCYST -AR, MCYST -LA, MCYSTLF, MCYST-LW and MCYST-YR were received from Calbiochem (U.S.A.) and Sigma (U.S.A.), and the other standards - from Dr. Karina Sivonen's laboratory (University of Helsinki, Finland). The following SPE cartridges were used: Bakerbond C18. SAX, DEA, NH2, CN (1000 mg, J.T. Baker, U.S.A.). AU chemicaIs used in the experiments were of analytical grade (J.T. Baker, U.S.A., and Metek, Germany). In all experiments, expendable equipment was used [37]-[41].
22
A.K.M.
KABZIŃSKI et al.
2.3. EXTRACTtON AND CLEAN-UP METHODS
The water sampIes (LOOO cnr') were filtered to remove mechanical inorganic and organie polIutants (0.47 urn GF52 filter. Schleider and Schnell, Germany), and then separated and partially prepurified by SPE method (SPE-12G, J.T. Baker, U.S.A.). SPE microcolumns were conditioned by isopropanol (10.0 cnr'), ethanol (10.0 crrr'), methanoI (10.0 crrr') and deionized water (10.0 cm'). Just after the sample preconcentration, rnicrocolurnns were rinsed with deionized water (10.0 crrr'), methanoI (10.0 crrr'), ethanol 00.0 crrr') and isopropanol (10.0 cm'). The heavy alcehol fractions were collected and evaporated at inert gas flow at a room temperature. The sampies were suspended in deionized water and then separated by SPE in NH2 and SAX microcolumns. After evaporation the samples were dissolved in chromatographic buffer [37]-[41J.
2.4. CHROMATOGRAPHIC
ANAL YSIS
After preconcentration using SPE technique, the water sarnples were separat ed by RP-HPLC method (HP 1050 with UVIVIS detector from Hewlett-Packard, U.S.A., and HPLC 600E with 990 DAD detector from Waters, U.S.A.) in columns, .types C18 (columns Spherisorb 5S ODS2 of 100x4.0 mm ID and 250x4.0 mm ID, equipped with precolumn CI8 of 4x4.0 mm m from Hewlett-Packard, U.S.A.; column Resolve C18 of 300x3.9 mm m from Waters, U.S.A., and Econosil CI8 of 250x4.6 mm ID from AlItech, U.S.A.) with detection at 240 nm and the volumes of injection loops of 20.0 and 250.0 mrrr'. The sampIes were separated by gradient and isocratic elution with application of acetonitrile, methanoI, arnrnonium-acetate buffer, phosphate buffer and sodium sulfate at a flow rate of 1.0 cm3/min [37J-(41).
2.5. AMINO ACIDS ANALYSlS
In order to make an additional identification, standards ofmicrocystins and toxins from algae responsible for blooms and water sampies were determined by amino acids analysis. Standards and purified sampIes of toxins were hydrolyzed with 6.0mol/dm3 HCl in the vapour phase at 110 "C for 24 hours and the released amino acids, after precolumn derivatization with phenyl isothiocyanate, were analyzed with the HPLC Waters Pico Tag system CD.S.A.). The amino acid derivatives were fed into a column of C18 type (150x 3.9 mm m, Waters, U.S.A.) and eluted using 0.14 mol/dm3 sodium acetate with the gradient of 0-60% acetonitrile for 15 min and at 38 "C, The eluted com-
Ozonation-based
removal
ofmicrocystin
from drinking water
23
2.6. OTHER ANAL YTICAL METHODS
MetaIs were determined with atomie absorption spectrometry (AAS) (SPECTRA 250 Plus - Varian, U.S.A.) with hydride generation and ETC countershaft and also with ATC socket. In alI analyses, acetylen e, nitrogen suboxide, argon for chromatographic analysis were used.Calibration lines for nickel, zinc, cadmium and lead were tested in the range of 0.0001-0.1 mg/drrr' with program of analysis: (a) dryness (30 s, 150 OC), (b) carbonization (30 s, 600 OC), (c) atomization (7.5 s, 2400 OC), (d) combustibility (3.0 s, 3100 "C). Other metaIs such as calcium, magnesium, copper and iron were determined spectrophotometrically according to PoIish Standards [44]-[48]. Ali biogenic substances we re determined according to PoIish Standards: ammonium nitrogen colorimetrically with indophenol bIue [49], nitrate(V) nitrogen colorimetrically with sodium salicylate (50], nitrate(lll) nitrogen colorimetrically with sulfanilic acid and Cleve acid (modified) [51], dissolved phosphoranes colorimetrically with molybdenum blue and tin(II)chloride as reducer [52J, total phosphorus [53] and total organie carbon (TOC) [54]. Use was made of spectrophotometer Metertek SP-830 with an optical patb of 1.000 cm. pH of water was measured according to [55] (pH-meter N-51n Feleko-Poland), and the concentration of dissolved oxygen in water was determined iodometrically according to [56]. Atotal concentration of biomass of cyanobacteria, phytoplankton and a total mass of plankton (cyanobacteria + phytoplankton + zooplankton) were determined according to Polish Standard under the inverted microscope MOD-2 [57]-[59]. The sampIes were treated with Lugol's solution modified by Utermohl. Measurements were carried out in the volume of 5, 10, 20 crrr' at the concentration lower than 10000 cells/cm3 and in volume 2.0 crrr' at the concentration higher than 10000 cells/crn'. Cyanobacteriał species were determined and the size of their cells was estimated. Total biomass was calculated according to the formuła: B = 1O-6xVxN where: B - the biomass of phy toplankton [mg/dm"], V - the volume of microorganisrns [~m3] and N - the number of microorganisms [number/cm']. Statistical analysis was carried out with Excel from Office 2000 (Microsoft, Poland), Statgraphics Version 3 (Manugustic Inc., U.S.A.) and by Statistica program (Stat Soft, U.S.A.).
3. RESULTS AND DISCUSSION The results of MCYST-LR removal in 2001 are given in table 5 and in figure L The mea n reduction in rhe concentration of MCYST -LR and other isoforms of microcystin in surface water in 1998-2001 is given in tables 6 and 7, respectively. The relationships between the concentration of MCYST-LR after its reduction and the
24
A.K.M.
KABZIŃSKI et al.
Tabłe5 Efficiency of MCYST-LR removal by chlorination and ozonation from Sulejów artiticial lake water in 2001 The date ofsampłe collection
Content of MCYST-LR Kalinko (water after ozonation)
Bronisławów (surface water)
Łódź-Chojny (tap water)
[~gldm3]
[%]
[~gldm3]
[%]
[~gldm3]
[%]
1.69 1.23
100.0 100.0 100.0 100.0 100.0 100.0 100.0
0.23 0.13 0.44 0.09 0.26 0.11 0.16
13.6 10.6 19.5 14.7 18.4
0.18 0.07 0.26 0.05
10.6 5.7 11.5
100.0 100.0
0.16
7.6 13.2 12.5
0.1ł
20.0
28-31.08.200 I 4-7.09.2001 11-14.09.2001 18-21.09.2001
2.26 0.61 1.41 1.45 1.21 1.28
25-28.09.2001 2-5.10.200 l 9-12.10.2001 16-19.10.2001 27-30.11.2001
0.55
0.17 0.06 0.11 0.07 0.09
Yiełds of tinał reduction of MCYST-LR [%] 89.3 94.3 88.5 91.8
8.2 12.1
87.9 95.8 90.9
4.1 9.1 5.5 16.4
94.5 83.6
2.5
a:: ...J 2
~ :::e~ _J>' o c
E
1.5
"tI
~} c
Gl U C
o
0.5
El Łódź·Chojny
o
O Bronisławów
!ł.
II Kalinko
c;; co
'"
(\j
"o
91
95
•
.'
CI)
::2: "6
c
o
U :l "O
,
89
y=7,12x+75,16 R2 = 0,3805
•
.•,
•
2
2,5
87
(])
lI:
85 1,5
3
b)
~
99
c
o
~
97
e
•
(])
o c
95
o lI: ...J
93
~ CI) >o
•
•
o
.
-
91
::2:
y = 0,4549x + 90,431 R2= 0,0259
•
•
"6
c o
89
•
''0
:l
"O
•
87
(])
c; 85 1
1,5
2
2,5
3
3,5
4
4,5
3
03 [mg/dm j
Fig. 3. The correlations between final efficiency of MCYST-LR removal and to tal doses ot"CI02 (a) and 03 (b) in treatment process
5
Ozonation-based removal oj microcystin from drinking water
31
oxidation ofeyanobaeterial toxinswith ozone always compete with the reactions of oxidation of other organie compounds.BERNAZEAU [61] claimed that 500 ug/dm' MCYST -LR could be oxidized (99%) with 0.2 mg 0y'dm3 over 4 minutes in the water free of organie compounds, but the presence of these eompounds (500 ug/dm') reduced the removal efficiency by 50% at the dose of 0.5 mg 0y'dm3 after 10 minutes, Additional doses of ozone (1.0--3.7 mg/dm') might be necessary for destroying cyanobacterial eells when their eoncentration ranged between 1x104 and 2.05x106 (30--100% removal) [28], [32], [62]. The coneentration of ozone in a pretreatment system for the water from Sulejów reservoir was higher by about 1.5-4.0 mg/dm'. In an initial step, Cl02 was added in the concentration range of 1.0--2.5 mg/dm' (table 8). Afinal MCYST -LR destruction of 84-96% was obtained for a cyanobacterial whose biomass ranged fromO to 1.009 mg/dm' and plankton of the biomass between 0.741 to 7.235 mg/dm'. In alI the periods, the eoneentration ofresidual ozone varied between 0.02 and 0.11 mg/dm' (table 8). During this study, a mean reduction in MCYST-LR eoncentration ranged from 89 to 93% and was higher than the results reported in literature. The removaI of other MCYSTs ranged between 59 and 97% (a mean of 81.7 +/- 13.3%) and was lower than that of MCYST-LR (table 7), but no comparable literature data were found. The efficiency of oxidation with ozone is considerably influenced by pH of water, because the oxidation potential is lower at alkaline medium reaction (1.24 V) than at acidic reaction (2.07 V) [28]. The presence of other organie and inorganie constituents in water during the ehlorination and ozonation as well as the eoneentrations of oxidants ean be important as well. We found positive correlations between physicochemical parameters and eoneentrations of CI02 and efficiency of MCYST-LR reduction in treated water (tab le 9). The significant correlations were found between the: hardness (r -0.5713), Ca(ll) (r +0.4584), Mg (II) (I' -D.6898), Pb (I' = +0.4226) and for CI02 (r = +0.5910) and removal of MCYST-LR. We did not find any correlations between pH (r = +0.2147), total organie earbon (TO C) (r = -0.2889), biomass (r= -D.0480) and ozone concentration (r = -D.0596) and. removal of MCYST -LR. The correlations between biomass, TOC, pH and 03 concentration may not have been observed due to a relatively high concentration of 03 being higher than in previous studies. The concentration of ozone was so high that organie substances had no influence on the .removal of MCYSTs from water, In aIl experiments, pH was higher than 7.5 (7.95-8.20), but under these conditions, with an oxidative potential of 1.24 V, the concentration of ozone was sufficient to obtain 80-90% efficiency of MCYST oxidation. The eorrelations between the ozon e and CI02 doses and the effieiencyof MCYST removal prove that both preoxidation and destruction of cyanobacterial eells with CIO:! were very effective. As with ozone, the efficieney of MCYST oxidation with chlorine dioxide greatly depends on pH [28]. The influence of Ca(II), Mg(ll) and Pb(ll) ions on MCYST removal is more difficult to explain, hence the experiments should be repeated.
=
=
=
32
A.K.M.
KABZIŃSKI et al.
We also tested the preconcentration of metaIs during treatment process. Only Zn(II), Ca(II) and Ni(ll) ions were preconcentrated during this process (table 10), but at Łódź-Chojny pumping station the eontent of these metaIs was lower than thepermissible limits laid down in Polish Standard of Ministry of Health. Based on the results obtained the following conclusion can be drawn: 1. The final efficiency of MCYST ~LR and other MCYST isoforms removal after ozonation ranges between 88.9 and 92.6% and between 58.5 to 96.7%, respectively. 2. No correlations between yields of ozonation and the doses of ozone applied (r = -0.0596) were found, thus higher doses than those used in this study may be needed to oxidize MCYSTs and other organie substances, even in alkaline medium (pH 7.95-8.20). 3. There was found alittle correlation (r = +0.5910) between the doses of C102, used for an initial oxidation of eyanobacterial cells and the efficiency of MCYST removal from surfaee water after cyanobacterial cell destruction. 4. Hardness, concentration of Ca(H), Mg(II) and Pb(1I) ions and amount of MCYSTs removed from water appeared to be correlated during oxidation. 5. During treatment process no toxic concentration of metaIs in water was observed.
REFERENCES [1] FRANCIS G., POiSOIlOIlS Australian lakes, Nature (London), 1878, 18, 11-12. [2] CODD G.A., STEFFENSD.A., BURCH M.D., BAKER P.D., Toxic blooms of cyanobacteria in We Alexandria, Soutn Australia - Learning from history. Aust. 1. Mar. Freshwater Res .• 1994, 45, 731-736. [3] CODD G.A., Cyanobacterial toxins: occurrence, properties and biologlcal significance, Water Sci. Techno!., 1995,32,149-156. [4] TISDALE E.S., Epidemie oj intenstinal disorder in Charleston W. Va., occurring simultaneously will! unprecedented water supply conditions, Am. 1. Pub. Health, 1931, 21, 198-200. [S] ZILBERG B., Gastroenteritls in Salisbury European children - a five year study, Cent. Afr. J. Med., 1966, 12, 164-168. [6] BOURKE A.T.C., HAWES R.B., NEILSON A., STALLMAN N.D., An outbreak oj hepatoenteritis (the Palm Island mystery disease} possibly caused by algal intoxicatlon, Toxicon Suppl., 1983, 3, 45-48. [7] FALCONER I.R., BERESFORD A.M., RUNNEGAR M.T.C., Evidence oj liver damage by toxins from b/OOTIIS of the blue-green algae Microcystis aeruginosa, Med. l. Aust., 1983, l, 511-514. [8] YOSIIIZAWA S., MATSUCHIMA R., WATANABE M.F., HARADA K.I., ICHlHARA A., CARMICHAEL W.W" FlIJlKI H .. lnhibition oj protein phosphatases by microcystin and nodularin associated witli hepatotoxicicty, 1. Cancer Res. Clin. Oncol., 1990, 116,609-614. [9] ERIKSSON J.E.. TOIVOLA D .. MERILUOTO I.A.O .. KARAKI H .. HAN Y.G .. HARTSHORNE D., Hepatocyte deformation induced by cyanobacterial toxins rejlects inhibition oj protein phosphatases, Biochem. Biophys.Res. Commun., 1990, 173, 1347-1353. [IO] MACKJNTOSH C., BEATTIE K.A., KWMPP S., COHEN P., CODD G.A., Cyanobacterial microcystin-Llł is a patent and specific inhibitor oj protein phasphatases J and 2A Jor both mammals and higher plan/s, FEBS Lett., 1990, 264, 187-192.
Ozonation-bascd
[II]
removal of microcystin from drinking water
33
NISHIWAKI-MATSUSHIMA R .. OBTA T., NISHlWAKI S., SUGANAMA M., KOBYAMA K., ISHlKAWA T., CARMICHAEL W.W.,
FUJlKI H., Liver tutnor promotlon. by cyanobacterial
cystln-LR, l. Cancer
Res. Clin. Oncol..
cyclic peptide toxin micro1992, 118. 42(}....424. [12] FUllKI H .• SUGANUMA M., Tumor promotlon by inhibitors of protein phosphatases l and 2A: the okadoic acid class compounds, Ady. Cancer Res., 1993,61, 143-194. [13] OHTA T .• SUEOKA E., KOMARI A., SUGANUMA M., NISHIWAKI R .• TATEMATSU M., KIM S.1., CARMICHAEL W.W., FUJlKl K., Nodularin a patent inhibitor of protein phosphatasees l and 2A is a /lew environmental caroinogen in mate F344 rat liver. Cancer. Res., 1994, 54, 6402-6404. [14] JOCHIMSEN E.M., CARMICHAEL W.w., CARDO D.M., COOKSON S.T., HOLMES C.E.M., ANTlJNES B.C.. FIUIO D.A.M., LYRA M.D., BARRETO V.S., AZEVEDO S.M.F.O .. JARVIS W.R., Liver [ailure and death after exposure to microcystins at a haemodialysis center in Brazil. New Eng. 1. Med., 1998,338,873-878. [15] LAMBERT T.W., HOLMES C.F.B., HRUDEY S.E., Microcystin class of toxins: heahh ejJects and safety of drinking water supplies, Environ. Rev., 1994.2, 167-186. [16] WHEELER R.E .• LACKEY J.B., SCIIOTT S., A contribution to the toxicity of algae, Publie Hlth. Rep., 1942,57. 1695-1701. [17] HOFI'MANN J.R.H., Removal of Microcystis toxins in water purification process, Water S.A., 1976, 2,58-60. [18] MONTEll AJ., Municipal drinking water treatnient procedures for lasie and odour abatement - a review. Water. Sei. Technol., 1983, 15,279-289. [19] H1MBERGER K., KElJOLA A.M., HUSVIRTA L., PYYSOLA H., SIVONEN K., The effect of water treatment processes on tlie renioval of hepatotoxins [rom Micracystis and Oscillatoria cyanobacteria: alaboratory study, Water Res., 1989,29.979-984. [20] FALCONER I.R., RUNNEGAR M .• HUYN V .• Effectiveness of activated carbon in theremoval of algal toxins [ram the potable water supplies: a pilot plant investigation, 1983, Xth Federal Convention 01' the Australian Water and Wastewater Association. . [21] FALCONER I.R., RLJNNEGAR M., BUCKLEY T., HUYN V., BRADSHAW P., Using activated carbon 10 retnove taxicity from drinking water containing cyanobacterial blooms, J. Arn. Wat. Wks. Assoc., 1989,81,102-105. [22] KEIJOLA A.M., H1MBERGER K., ESALA A.L., SIYONEN K., HUSVIRTA L.. Removal of cyanobacterial toxins i/l water treaunent processes: laboratary and piłot-scale experiments, Tox. Assess., 1988,3, 643-656. [23] NICHOLSON B.C., ROSITANO L, BURCH M.D., Destruction of cyanobacterial peptide hepatotoxins by chlorine and chloramines, Water Res., 1994,28, 1297-1303. [24] NICHOLSON B.C., ROSITANO I., HUMPAGE A .. BURCH M., Removal of algal toxins in water treatment process, Australian Water and Wastwater Assoc., 1993, 10,327-331. [25] CHOW C.W.K., HOUSE J., VELZEBOUR R.M.A., DRIKAS M., BURCH M.D., STEFFENSEN DA, The effect of ferric chloride flocculation on cyanobacterial celt, Water Res., 1998, 32, 808-814. [26] TAKENAKA S., TANAKA Y., Decomposition of cyanobacterial microcystins by ironilll) chloride. Chemosphere, 1995,30, 1-8. [27] TAKENAKA S., TANAKA Y., Behavlor of microcystins and decomposition produet in water treatment process, Chemosphere, 1995,31. 3635-3641. [28] ROS1TANO J., NICHOLSON B.C., PIERONNE P., Destruction of cyanobactreial toxins by ozone, Ozon e Sci. Engng., 1998,20,223-238. [29] ROSITANO J., NEWCOMBE G.• NICHOLSON B., SZTAJNBOK P., Ozonation of NOM and algal in [our treaied waters. Water Res., 2001, 35, 23-32. [30] HART 1., SCOTT P., Microcystin-Llł removal from water, Report FR 0367, Foundation for Water Research, 1993, Buckinghamshire, Marlow.
A.K.M.
34
KABZINSKI et al.
[311 HART J .. FAWELL lK .. CROLL B .• The fale of botn intra- and extracellular
water treatment. 1997. Speciał Subject. [32] CARLILE P.R .. FUr/hel' studies lO investigate microcystin-Lłł Report FR 0458. Foundation
toxins dl/ring drinking removal from water.
and anatoxin-a
for Water Research. 1994. Buckinghamshire.
Marlow.
133J FAWELL J.K .. HART 1.. JAMES H.A., PARR W .. Blue-green algae and their toxins - analysis, treat-
ment and environmental eontroi. Water Suppły. 1993. 11(3/4). 109-115. The destruction of cyanobacterial peptide toxins by oxidants used in water treatment,
[34) ROSITAr-:Ol.
Report No. 10. Urban Water Research Association
of Australia,
1996. Melbourne.
135J CROLL B., HART l .. Algal toxins and customers. UKWIR-AWWARF ence. Philadelphia.
October
14-16.
Transfer
Confer-
1996.
[36] ROBERTSON P.KJ .• LAWTON L.A .. CORNISH BJ.P.A .. JASPERS M .. Processes
struction of microcystin-LR
Vic.
Technology
by TiO] photocatalysis.
J.
Photochem.
Photobiol.
Influencing the de-
(A): Chemistry.
1998.
116.215-219. f37] KABZIŃSKI A.K.M.,
JlJSZCZAK R .. MIĘKOS E .• TARCZYŃSKA M., SIVONEN K., RAPALA 1.. The [irst
report about presence of cyanobacterial
toxins in Polish lakes, Polish 1. Environ.
Stud .. 2000. 9.
171-178. [38J KABZINSKI A.K.M.,
GRABOWSKA H., JlJSZCZAK H .. SZCZlJKOCKl D.E., SZCZYTOWSKI K .• The influ-
ence of pollutions al SI/lejów artificial lake for biosynthesis of cyanobacterial bacterial toxins: (I) macrabiogenie substances (submitted for publication).
biomass al/d cyano-
[39) KABZINSKI A.K.M .. GRABOWSKA H., JUSZCZAK H .• ZAWADZKA A., SZCZUKOCKl D.E .. SZCZYTOWSKI
K.. The influence of pollutions m SI/lejów artijieiallake for biosynthesis of cyanobacterial biomass and cyanobacterial toxins: (II) biogenic and toxic metais (submitted for publication). [40] KA13Z1NSKIA.K.M., JUSZCZAK R .. DZIEGIEĆ l, Analysis of cyanobacterial toxins in Poland - present situation
in period 1998-2001
[41) KABZIŃSKI A.K.M.,
(submittcd
for publication).
The problems witli analysis of cyanobacterial
toxins by SPE and HPLC lech-
niques (submitted for publication). NAMIKOSHl M .• First report of microcystins Microcystis aeruginosa. J. Appl. Phycol., 1994, 6,
[42) AZEVEDO S.M.F.O .• EVANs W.R .• CARMICHAEL W.W.,
from a Brazilian iso/me of the cyanobacterium 261-265.
[43) KRISIINAMlIRTHY T.. CARMICHAEL W.W .. SARVER E.W., Toxic peptides [rom [reshwater
[44] [45] [46] [47]
cyanobacteria (blue-green algae). Isolation. purification, and characterization of peptides [ram Microcystis aeruginosa and Anabaena flos-aquae, Toxicon, 1986. 24. 865-873. Polish Standard: Omaczanie ogólnej twardosci wody metodą wersenianową. PN-7l. C-04554/02. Polish Standard: Badanie zawartoset wapnia metodą wersenianową. PN-91. C-0455 I/Ol. Polish Standard: Badanie zawartości magnezu metodą wersenianowq. PN-75. C-04562/01. Polish Standard: Badanie zawartości miedzi z użyciem dietylodotiokarbaminianu sodu. PN-C04611-2.
(48) Polish Standard: Badanie zawartoset żelaza z użyciem l,lO-fellantroliriy.
PN-90, C-04586/04.
[49] Polish Standard: Badanie zawartości jonów amonowycli z użyciem indofenolu. PN-76. C-04576/0 I. [50] Polish Standard: Omaczanie [51) [52] [531 [54)
[55]
azotu atotanowegofV) w wodzie metodą kolorymetryczmnq z salicylanem sodowym. PN-82. C-04576/08. Polish Standard: Omaczanie azotu azotanowegotlll] metoda kolorymetryczną z kwasem sulfanilowym i kwasem Cleve 'a. PN-73, C-04576. Połish Standard: Oznaczanie rotpusictonycli onofosforanow kolorymetryczna me/odą molibdenianową z chlorkiem cynyill) jako reduktorem. PN-89, C-04537/02. Polish Standard: Oznaczanie fosforn ogólnego. PB-91. C-04537/09. Polish Standard: Omaczanie ogólnej zawartości węgla organicznego (OWO). PN-C-04633-3. Polish Standard: Omaczanie pll wody. PN-90, C-04540/01.
Ozonation-based
removal oj microcystin from drinking water
35
[56] Polish Standard: Oznaczanie tlenu rozpuszczonego metodą jodometryczną. EN-258 l 3: 1992. [57] Polish Standard: Omaczanie liczebności fitoplanktonu za pomocą mikroskopu odwróconego. PN87. C-0555 l. [58] Polish Standard: Woda i ścieki. Pobieranie próbek do badali biologicznych. Postanowienia ogólne i zakres norm. PN-86. C-05550/0 l. (59] Polish Standard: Woda i ścieki. Pobieranie próbek do badań biologicznych. Pobieranie próbek fitoplanktonu. PN-86. C-05550/02. [60] ROSITANOl .. NICHOl.sONB., Waler treatment techniques jor the removal oj cyanobacterial toxins from water, Australian Ccntrc for Water Quality Research, 1994,2/94. [61] BERNAZEAU F.. Can microcystin enter drinking water distribution system. Am. Water Works Assoc. Res. Found .. 1994.8, 115-118. [62] HOGERS., DIETRICHD., HITZAELDB.. EjJect oj ozonation in drinking water treatment on the removal of cyanobacterial toxins, Toxicol. Sci., 1999,48,33-39. [63] CODD G.A., WORD c.J., BELL S.G., Cyanobacterial toxins: occurrence, modes oj action. healtb aspec/s and exposure rates, Arch. Toxicol. (Suppl.), 1997, 19,399-410. [64] KOTAKB.G., Occurrence and healtlt significance oj algal toxins in Alberta surface waters. Proc. Alberta Lake Manag. Soc., 1991. 1/2, 1-8. [65] KABZIŃSKIA.K.M., JUSZCZAKR., DZIEGIEĆ1.. The problems witli determination oj cyanobacterial toxins in lakes water and drinking water and also in biological materiał, Przegląd Geolog., 2001. 49, 995-996.
USUWANIE MIKROCYSTYNY Z WODY PITNEJ METODĄ OZONOWANIA NA PRZYKŁADZIE ZBIORNIKA ZAPOROWEGO W SULEJOWIE Sinice mogą produkować toksyny, związki pogarszające smak i dające nieprzyjemny zapach, obniżając w ten sposób jakość wody. Usuwanie komórek sinicowych wraz z ich produktami wewnątrzkomórkowymi w czasie procesu uzdatniania wody zmniejszy stężenie substancji smakowych i zapachowych oraz toksycznych metabolitów w uzdatnianej wodzie. Przedstawiono ozonowanie w stacji wstępnego uzdatniania wody znajdującej się w pobliżu zbiornika zaporowego w Sulejowie. Stężenie MCYST-LR i innych izoform tej hepatotoksyny w wodzie oznaczano techniką RP-HPLC po wstępnym oczyszczaniu i zatężaniu próby metodą SPE.
