Montserrat
Filella
*ab
aInstitute F.A. Forel, University of Geneva, Route de Suisse 10, CH-1290, Versoix, Switzerland. E-mail: montserrat.filella@unige.ch
bSCHEMA, Rue Principale 92, L-6990, Rameldange, Luxembourg
First published on 15th December 2009
Like all elements of the periodic table, bismuth is ubiquitously distributed throughout the environment as a result of natural processes and human activities. It is present as Bi(III) in environmental, biological and geochemical samples. Although bismuth and its compounds are considered to be non-toxic to humans, its increasing use as a replacement for lead has highlighted how little is known about its environmental and ecotoxicological behaviour. In this first critical review paper on the existing information on bismuth occurrence in natural waters, 125 papers on fresh and marine waters have been collated. Although the initial objective of this study was to establish the range of the typical concentrations of total dissolved bismuth in natural waters, this proved impossible to achieve due to the wide, and hitherto unexplained, dispersion of published data. Since analytical limitations might be one of the reasons underlying value dispersion, new analytical methods published since 2000—intended to be applied to natural waters—have also been reviewed. Disappointingly, the detection limits of the bulk of them are well above those required; they are thus of limited usefulness. Analysis of the existing information on bismuth in secondary references (i.e., books, review chapters) and on its chemical speciation in seawater revealed that the uncritical reproduction of old data is a widespread practice.
![]() Montserrat Filella | Montserrat received her PhD in Chemistry from the University of Barcelona in 1986. She teaches Environmental Chemistry at the University of Geneva, where she arrived in 1987. Since 2007 she also works in the development of a society specialised on fundamental research in environmental chemistry in Luxembourg. She is an IUPAC fellow and member of a number of scientific societies. Her main research interests focus on the understanding of the physicochemical processes regulating the behaviour of chemical elements in environmental and biological compartments. The three main axes of her research concern the study of: colloids in natural waters, natural organic matter and Group 15 elements. |
Environmental impactBismuth has been qualified as an “amazingly ‘green’ environmentally-minded element”. In the early 1990s, research began on the evaluation of bismuth as a non-toxic replacement for other more noxious elements, particularly lead. The introduction of bismuth in some of these applications, and in particular the approval of bismuth-tin shot for waterfowl hunting, has been accompanied by the ‘discovery’ that actually very little is known about the ecotoxicology of the element. Similarly, its environmental chemistry remains poorly understood. As a first step to identify the areas of environmental bismuth chemistry that need to be preferentially addressed, this study critically analyses published values of total concentrations in surface waters as well as the scarce existing information on bismuth speciation in aquatic systems. |
Bismuth has no known biological role. It is an element which is relatively non-toxic to humans in comparison to the metals and metalloids surrounding it in the periodic table (i.e., polonium, tellurium, antimony, tin and lead). However, bismuth is toxic to some prokaryotes, and bismuth compounds have been used for more than 200 years to treat ailments resulting from bacterial infections.
Little information is available on the transformation and transport of bismuth in the different environmental compartments and even information on total bismuth content in the various environmental media is scarce and often contradictory, as evidenced in this study which gathers and analyses published values of bismuth concentrations in seawater and freshwater.
Systema | Complementary information | Dissolved Bib original units | Units | Dissolved Bi/ng L−1 | Particulate Bi | Sample acidification | Filtration | Experimental techniquec | DLd/ng L−1 | Type of studye | Ref. | |
---|---|---|---|---|---|---|---|---|---|---|---|---|
a International country codes follow the ISO 3166 convention; specific sampling dates are only given when they are needed to differentiate samples. b n = number of analysis; BDL = below detection limit; DL = detection limit; CL = 95% confidence limits; RSD = relative standard deviation. c See corresponding list for meaning of abbreviations. d DL = detection limit. e Type of study: BI = environmental study devoted to Bi only, ENV = environmental oriented study but not devoted to Bi only, ANAL = analytical method development study where Bi concentrations have been measured in real samples but no ancillary environmental data about the system are given. | ||||||||||||
Gullmar fjord, SE, summer 1937 | 0.2 | μg L−1 | 200 | — | not mentioned | Co-precipitation | — | ENV | 12 | |||
Spectrographic method | ||||||||||||
South African coastal water | 0.017 | mg tonne−1 | 17 | 0.1 M in HCl | sedimentation bottle + cotton-wool plug | Anion-exchange (Amberlite IR-400, 100 days, 250 L) of the 0.1 N HCl acidified sample | not given | ANAL | 13 | |||
Emission spectroscopy of evaporated and ashed resin | ||||||||||||
English Channel (50° 02′ N 4° 22′ W), surface water | 0.024, 0.026 (n = 2) | μg L−1 | 24, 26 | 0.1 M in HCl | Whatman glass-fibre filter (GF/B) | Anion exchange (De-Acidite FF) of the 0.1 N HCl acidified sample | not given | ANAL | 14 | |||
Irish Sea, surface water | 2 samples | 0.042, 0.035 | 42, 35 | |||||||||
North Atlantic (45° 07′ N 7° 38′ W): | Photometric determination with dithizone | |||||||||||
surface water | 0.033 | 33 | ||||||||||
2000 m depth | 0.015 | 15 | ||||||||||
Jervis Bay, New South Wales coast, AU | 3 samples collected 4 months apart | 0.21 ± 0.02 (n = 2) | μg L−1 | 210 | 0.011 ± 0.002 (n = 2) | pH < 2 (0.02 M in HCl) | 0.45 mm Millipore filter (HAWP 047 00) | ASV on a glassy carbon mercury coated electrode | not given | ANAL | 15 | |
0.13 ± 0.02 (n = 2) | 130 | <0.005 (n = 2) | Particulate digestion: filter wet-ashing with 2 mL 15 M HNO3 and 1 mL 72% HClO4 | |||||||||
0.043 ± 0.02 (n = 2) | 43 | <0.005 (n = 2) | ||||||||||
All in μg L−1 | ||||||||||||
Boston Light-Ship, US | 0.015 (CL: 43%, n = 3) | μg kg−1 | 15 | 0.1 M in HCl | not mentioned | MCGE-ASV (pH 0.5–1.5) | 4 | ANAL | 16 | |||
Pacific deep water, Baja, California, US | 0.040 (CL: 42%, n = 3) | 40 | pH 1.67 (HCl) | |||||||||
Bahia Honda Key, FL, US | 4 samples | 0.090 (CL: 6%, n = 3) | 90 | 1 M in HCl | ||||||||
0.086 (CL: 31%, n = 3) | 86 | |||||||||||
0.094 (CL: 4%, n = 3) | 94 | |||||||||||
0.080 (CL: 25%, n = 3) | 80 | |||||||||||
New South Wales and Queensland coastal waters, AU: | μg L−1 | 0.05 M in HCl | 0.45 μm Millipore filter (HAWP 047 00) | ASV on a glassy carbon mercury coated electrode | not given | BI | 17 | |||||
Botany Bay | 0.11, 0.11 | 110, 110 | 0.002 | |||||||||
Jervis Bay | 0.045, 0.043 | 45, 43 | 0.002 | Particulate digestion: filter wet-ashing with 2 mL 15 M HNO3 and 2 mL 72% HClO4 | ||||||||
Jervis Bay | 0.045 | 45 | — | |||||||||
Jibbon Beach | 0.018, 0.021 | 18, 21 | <0.001 | |||||||||
Jibbon Beach | 0.041 ± 0.003 (n = 7) | 41 | 0.005 | |||||||||
Jibbon Beach | 0.038 | 38 | — | |||||||||
Queensland | 0.12, 0.10 | 120, 100 | <0.001 | |||||||||
All in μg L−1 | ||||||||||||
Standard sea water sample (origin unknown) | <0.01 (DL) | ppb | <10 | — | not mentioned | ASV on a glassy carbon mercury coated electrode | 10 | ANAL | 18 | |||
North Sea, off the Belgian Coast, 3 m depth | 5 samples | 0.20, 0.68, 0.55, 0.20, 0.28 | ppb | 200, 680, 550, 200, 280 | not mentioned | 0.8 μm Millipore filter | HMDE-DPASV (pH 1, 1.2 M HCl) | 50 | ANAL | 19 | ||
Sea water, 34° 25′ N 133° 54′ E (Shibukawa, Okayama Prefecture, JP) | 0.010 ± 0.002 (n = 4) | μg L−1 | 10 | not mentioned | not mentioned | Flotation (surfactant: sodium dodecyl sulfate and sodium oleate) of Bi co-precipitated with iron(III) hydroxide | not given | ANAL | 20 | |||
HG-AAS | ||||||||||||
Kattegatt surface seawater: | pM | not acidified, NaOH added | not mentioned | Co-precipitation with Mg(OH)2, centrifugation (1200 rpm, 10 min) , centrifugation (1200 rpm, 10 min) | not given | ANAL | 21 | |||||
N 56° 33.3, E 12° 53.6 | 13 ± 7 (n = 8) | 2.7 | ||||||||||
N 57° 36.6, E 11° 53.4 | 7 ± 3 (n = 4) | 1.5 | ||||||||||
N 57° 38.9, E 11° 52.2 | 7 ± 1 (n = 4) | 1.5 | PSA | |||||||||
Pacific Ocean (17° 30′ N, 109° 00′ W), water depth 3550 m: | ng L−1 | pH 2 (HCl) | 0.45 μm Millipore filter | Precipitation with 6 M NaOH, decantation | 0.003 | ANAL | 22 | |||||
surface Oct 31, 1981 | 0.053 | 0.053 | HG-AAS | |||||||||
2500 m below surface Nov 3, 1981 | <0.003 (DL) | <0.003 | ||||||||||
Scripps Pier, La Jolla, CA, US: | ||||||||||||
Oct 15, 1981 | 0.052 | 0.052 | 0.13 (total) | |||||||||
Jan 4, 1982 | 0.085 | 0.085 | 0.29 (total) | |||||||||
San Diego Bay, San Diego, CA, US, Dec 18, 1981 | 0.63 | 0.63 | 2.0 (total) | |||||||||
Mission Bay, San Diego, CA, US, Dec 18, 1981 | 0.46 | 0.46 | 1.6 (total) | |||||||||
All in ng L−1 | ||||||||||||
Pacific ocean coastal waters, JP: | ng mL−1 | 10 mL HNO3 per 1 L sample | not mentioned in the English abstract | Extraction of the Bi- DEDTC complex in CCl4, rotary evaporation of the solvent, rotary evaporation of the solvent | 4 | ANAL | 23 | |||||
Hitachi | 0.026 | 26 | ||||||||||
Tkai | 0.032 | 32 | ||||||||||
Isozaki | 0.030 | 30 | GFAAS | |||||||||
Oarai | 0.025 | 25 | ||||||||||
North Sea (Belgian Coast) | same sample, several methods | 0.05 | μg L−1 | 50 | not mentioned | 0.45 μm filter | HMDE-DPASV, pH 1.15 | not given | ANAL | 24 | ||
0.05 | 50 | HMDE-DPASV + SO2 | ||||||||||
0.10 | 100 | HMDE-DPASV + UV + SO2 | ||||||||||
0.011 | 11 | RRDE-ASV, pH 1.15 | ||||||||||
0.014 | 14 | RRDE-ASV + SO2 | ||||||||||
0.13 | 130 | RRDE-ASV + UV + SO2 | ||||||||||
North Atlantic seawater (surface samples and profile down to 2800 m) | 19 samples | 12 ± 9 | pM | 2.6 | not acidified, NaOH added | not mentioned | Co-precipitation with Mg(OH)2, centrifugation (1200 rpm, 10 min), centrifugation (1200 rpm, 10 min) | 1 | BI | 25 | ||
PSA | ||||||||||||
Transect North Atlantic and Caribbean: | fmol kg−1 | yes but no details given | not mentioned | HG-AAS as in [22] | not given | ENV | 26 | |||||
Coastal waters | 250 | 0.052 | ||||||||||
Sargasso Sea | 340 | 0.071 | ||||||||||
Caribbean | 250 | 0.052 | ||||||||||
Both sides Panama Basin | <150 | <0.031 | ||||||||||
off Bermuda waters | 290 | 0.061 | ||||||||||
North Sea, off the Belgian coast, Jul 83 | 19 stations | <0.005 (DL) except close to the coast and in the vicinity of Scheldt estuary: | μg L−1 | not mentioned | not mentioned | HMDE-DPASV, RRDE-DCASV | 5 | ANAL | 27 | |||
0.005 – 0.014 (acid) | 5 – 14 | Two types of results depending on method used to destroy NOM: acid and UV | ||||||||||
0.070 – 0.150 (UV) | 70 – 150 | |||||||||||
Profiles in the North Pacific (coast of California out to the N of Hawaii) | surface (20 m) | 89 | fmol kg−1 | 0.019 | pH < 2 (4 mL 6 M HCl in 1 L sample) | not mentioned | Anion exchange (AG1-X2) of the 0.1 N HCl acidified sample | not given | BI | 28 | ||
94 | 0.020 | |||||||||||
99 | 0.021 | |||||||||||
113 | 0.024 | |||||||||||
152 | 0.032 | HG-AAS | ||||||||||
171 | 0.036 | |||||||||||
1000 m depth | 268 | 0.042 | ||||||||||
200 | 0.047 | |||||||||||
225 | 0.037 | |||||||||||
178 | 0.056 | |||||||||||
5500 m depth | 28 | 0.006 | ||||||||||
Profiles in several locations in the Atlantic | surface (10 m) | 453 | 0.095 | |||||||||
1032 m depth | 177 | 0.037 | ||||||||||
4855 m depth | 115 | 0.024 | ||||||||||
Coastal regions, CN | 1094 sampling stations | (0.95 ± 0.25)×10−11 | M | 2.0 | not mentioned | 0.45 μm filter | HMDE-ASV | not given | ENV | 29 | ||
(0.7 – 1.2)×10−11 | ||||||||||||
Tokyo Bay, JP: | ng L−1 | pH 2 (HCl) | not mentioned | Precipitation with 6 M NaOH, filtration (0.40 μm) | 1 ng (in?) | ANAL | 30 | |||||
16 Sep 1986 | 5 samples | 1.0, 2.1, 1.5, 1.0, 0.6 | 1.0, 2.1, 1.5, 1.0, 0.6 | |||||||||
8 Dec 1986 | 1 sample | 1.5 | 1.5 | HG-AAS | ||||||||
Coast of Heligoland | 12 ± 2 | ng L−1 | 12 | not mentioned | not mentioned | SW-ASV (glassy-carbon RDE) | 2 | ANAL | 31 | |||
Palaea Kameni hydrothermal waters, Santorini, GR | <0.8 (DL) | μg L−1 | <800 | not mentioned | not mentioned | Reference given (conference proceedings) | 800 | ENV | 32 | |||
Kanazawa City, JP: | ng L−1 | 18 mL HNO3 in 1 L sample | 0.45 μm Millipore filter | Preconcentration: sorption on thionalide-loaded silica gel | 100? | ANAL | 33 | |||||
Sai River | 2.4 | 2.4 | HG-AAS | |||||||||
Tatsumi canal | 3.4 | 3.4 | ||||||||||
Asano River | BDL | BDL | ||||||||||
Pacific Ocean (33° 17′ 33′′ N 134° 13′ 1′′ E), 2.7 km off-shore, 320 m depth | 0.161 (RSD: 2.2%, n = 3) | ng L−1 | 0.161 | pH 1.5 (HCl) | unfiltered | Solvent extraction: triisooctylamine in heptane, pH = 1.5 | 3 | ANAL | 34 | |||
Pacific Ocean (36° 57′ N 140° 51′ 53′′ E): | ||||||||||||
1 m depth | 0.453 (RSD: 2.1%, n = 3) | 0.453 | ICP-MS | |||||||||
99 m depth | 0.471 (RSD: 1.8%, n = 3) | 0.471 | ||||||||||
Isozaki coast (36° 22′ 40′′ N, 140° 37′ 56′′ E), JP | 1.6 (RSD: 6.9%, n = 4) | ng L−1 | 1.6 | 0.1 M in HCl | 0.45 μm Millipore filter (after acidification) | Solvent extraction: sodium diethyldithiocarbamate in xylene | 0.27 | ANAL | 35 | |||
Hitachi harbour (36° 28′ 27′′ N, 140° 37′ 50′′ E), JP | 1.6 (RSD: 6.2%, n = 4) | 1.6 | ETAAS | |||||||||
Seawater, Chiba, Katsuura City, JP | 0.0125 (RSD: 4.0%, n = 4) | ppb | 12.5 | not mentioned in the English abstract | not mentioned in the English abstract | Co-precipitation with zirconium hydroxide; filtration | 10 | ANAL | 36 | |||
DP-ASV | ||||||||||||
Buzzards Bay, MA, US | 0.038 pM | not mentioned | 0.2 μm filter | CFF: fraction 1 kDa–0.20 μm | not given | ENV | 37 | |||||
Evaporation, dissolution HNO3 | ||||||||||||
ICP-MS | ||||||||||||
NRCC NASS-3 (open seawater) | 0.014 ± 0.002 (n = 5) | ng mL−1 | 14 | — | VG-ETV-ICP-MS with in situ preconcentration in a Pt-coated GF | 3 | ANAL | 38 | ||||
Seawater (no details given) | 12 ± 2 | ppb | 12![]() |
0.1 M HNO3 | 0.45 μm Millipore filter (after acidification) | Preconcentration: polyurethane column packed with F2H2Dz | 10![]() |
ANAL | 39 | |||
Flameless AAS | ||||||||||||
Chinese certified seawater GBW(E) 080040 | 0.0036 ± 0.0005 (n = 6) | ng mL−1 | 3.6 | pH 2 (HNO3) | 0.45 μm Millipore cellulose membranes (probably after acidification) | Preconcentration: poly(acrylaminophosphonic – dithiocarbamate) fibre; elution and evaporation to near dryness | 0.155 | ANAL | 40 | |||
Coast of China, 1 m depth samples: | ng L−1 | |||||||||||
Tianjin seawater | 8.70 | 8.70 | ||||||||||
Dalian seawater | 8.10 | 8.10 | ICP-MS | |||||||||
Qingdao seawater | 3.09 | 3.09 | ||||||||||
Qinghuangdao seawater | 11.4 | 11.4 | ||||||||||
Chinese certified seawater GBW(E) 080040 | 0.0037 ± 0.0005 (n = 6) | ng mL−1 | 3.7 | pH 2 (HNO3) | 0.45 μm Millipore cellulose membranes (probably after acidification) | Preconcentration: sorption onto 8-hydroxyquinoline immobilized polyacrylonitrile hollow fibre membrane | 31 | ANAL | 41 | |||
Coast of China, 1 m depth samples: | ng L−1 | |||||||||||
Tianjin seawater | 8.85 | 8.85 | ||||||||||
Dalian seawater | 7.88 | 7.88 | ICP-MS | |||||||||
Qingdao seawater | 3.01 | 3.01 | ||||||||||
Qinghuangdao seawater | 11.9 | 11.9 | ||||||||||
Ise Bay (1 km off-shore Nagoya port), JP | 0.0017 | μg L−1 | 1.7 | pH 1 (HNO3) | 0.45 μm membrane filter | Preconcentration by chelating resin (Chelex 100) adsorption | 0.03 | ANAL | 42 | |||
ICP-MS | ||||||||||||
Less than 50% recovery | ||||||||||||
Sea water (no details given) | 6 samples | 0.54 ± 0.05 | μg L−1 | 540 | not mentioned | not mentioned | HG-ETAAS | 70 | ANAL | 43 | ||
0.30 ± 0.05 | 300 | |||||||||||
<0.24 | <240 | |||||||||||
<0.24 | <240 | |||||||||||
0.26 ± 0.05 | 260 | |||||||||||
0.33 ± 0.05 | 330 | |||||||||||
Bosphorous seawater | 0.0048 ± 0.0008 (n = 3) | mg L−1 | 4800 | 5 mL HNO3 added to an unknown sample volume | not mentioned | SPE: silica gel modified with 3-aminopropyltriethoxysilane | 800 | ANAL | 44 | |||
GF-AAS | ||||||||||||
Marmara Sea, near Istambul, TR | heavily polluted | 0.053 ± 0.002 (n = 5) | mg L−1 | 53![]() |
not mentioned | 0.45 μm Millipore cellulose membrane filter | SPE: Chromosorb-107 | 500 | ANAL | 45 | ||
GF-AAS | ||||||||||||
Ise Bay (1 km off-shore Nagoya port), JP | 0.00038 ± 0.00002 (n = 3) | μg L−1 | 0.38 | pH 1 (HNO3) | 0.45 μm membrane filter | Tandem preconcentration using a chelating resin (Chelex 100) | 0.05 | ANAL | 46 | |||
ICP-MS | ||||||||||||
Gulf of Bengal close to Pulicat Lake, IN: | μg L−1 | 5 mL HNO3 in 1 L sample | 0.45 μm cellulose membrane filter (after acidification) | SPE: piperidene dithiocarbamate-coated Amberlite XAD-7 resin | 1200 | ANAL | 47 | |||||
Sea water 1 | 1.4 ± 0.08 (n = 5) | 1400 | ||||||||||
Sea water 2 | BDL | ICP-MS | ||||||||||
Shibukawa Sea, Okayama, JP | 22.9 ± 0.5 (n = 5) | pg mL−1 | 22.9 | not mentioned | not mentioned | Preconcentration: glycine-type chitosan resin | 0.1 | ANAL | 48 | |||
ICP-MS | ||||||||||||
Shibukawa Sea, Okayama, JP | 0.023 ± 0.000 | ng mL−1 | 23 | not mentioned | not mentioned | Preconcentration: chitosan resin functionalized with CCTS-DHBA | not given | ANAL | 49 | |||
Shin Okayama Port, Okayama, JP | 0.018 ± 0.001 | 18 | ICP-AES |
Because of their possible strong influence on the reported results, filtration details are given when available (unfortunately, nearly 50% of the studies neglect to mention whether the samples have been filtered or not). The limit of detection of the analytical methods applied as well as information about acidification of samples are also provided, as they can help to evaluate the reliability of the associated results. As readily observed in Table 1, the dispersion of published results is very high. Even if extremely large values—very probably due to external contamination during sampling or analysis—are not considered, value dispersion remains high and cannot be accounted for by the fact that values from coastal zones, more prone to the effects of man-made pollution, have also been included in the table. Interestingly, there is no clear trend linking the concentration values with the year of publication nor, in particular, is any decrease in the measured concentrations observed, as is the case for other elements. On the basis of the published values, and considering the apparent quality of the different studies, it could be safely stated that bismuth was present in seawater at a 10–30 ng L−1 concentration level, if the often-referenced, and usually well-considered, values of Lee and co-workers22,26,28 were not about three orders of magnitude lower. Interestingly, these authors22,28 found a significant proportion of the total Bi, ca. 70%, in particulate form and reported fairly dynamic behaviour of the element in seawater. The predominant presence of bismuth associated to particles might help to explain Lee's low values but is of no assistance in determining whether other reported values are too high because they include some colloidal Bi as ‘dissolved’, which Lee also does partly by filtering at 0.45 μm, or whether Lee's preconcentration methods ‘lose’ some ‘dissolved’ bismuth.. 70%, in particulate form and reported fairly dynamic behaviour of the element in seawater. The predominant presence of bismuth associated to particles might help to explain Lee's low values but is of no assistance in determining whether other reported values are too high because they include some colloidal Bi as ‘dissolved’, which Lee also does partly by filtering at 0.45 μm, or whether Lee's preconcentration methods ‘lose’ some ‘dissolved’ bismuth.
Systema | Complementary information | Dissolved Bib original units | Units | Dissolved Bi/ng L−1 | Particulate Bi | Sample acidification | Filtration | Experimental techniquec | DLd/ng L−1 | Type of studye | Ref. | |
---|---|---|---|---|---|---|---|---|---|---|---|---|
a International country codes follow the ISO 3166 convention; specific sampling dates are only given when they are needed to differentiate samples. b n = number of samples; CV = coefficient of variation; RSD = relative standard deviation. c See corresponding list for meaning of abbreviations. d DL = detection limit. e Type of study: BI = environmental study devoted to Bi only, ENV = environmental oriented study but not devoted to Bi only, ANAL = analytical method development study where Bi concentrations have been measured in real samples but no ancillary environmental data about the system are given. | ||||||||||||
Waters from 15 regions of Siberia, RU | 2666 samples (Bi found in 13 samples) | 0.0001–0.0054 | mg L−1 | 100–5400 | not mentioned | not mentioned | Precipitation (sodium sulfide and aluminium hydroxide) | not given | ENV | 50 | ||
Spectrographic method | ||||||||||||
Antarctica highly saline lakes (McMurdo Oasis): | μg L−1 | not mentioned | not mentioned | pH 3 (HCl), oxidation with Cl2 gas, extraction with cyclohexane, tar ashing at 450 °C gas, extraction with cyclohexane, tar ashing at 450 °C | not given | ENV | 51 | |||||
Lake Vanda | 6.1 | 6100 | ||||||||||
Lake Bonney | 7.1 | 7100 | ||||||||||
Lake Fryxell | <2 | <200 | ||||||||||
Lake Joyce | 3.8 | 3800 | Spectrographic method | |||||||||
Lake Hoare W lobe | <2 | <200 | ||||||||||
Lake Hoare E lobe | <2 | <200 | ||||||||||
Lake Miramar, San Diego, CA, US | <0.15 | ng L−1 | <0.15 | <0.15 (total) | pH 2 (HCl) | 0.45 μm Millipore filter | Precipitation with 6 M NaOH, decantation | 0.003 | ANAL | 22 | ||
Rain Water, La Jolla, CA, US | 0.62 | 0.62 | 3.2 (total) | |||||||||
All in ng L−1 | HG-AAS | |||||||||||
Raw water | <0.05 (filtered 0.45 μm) | μg L−1 | <50 | 0.06 ± 0.03 (total) | pH 1.5–1.7 (HCl or HNO3) | 0.45 μm and 2 nm filters | Stripping voltammetry | not given | ENV | 52 | ||
<0.05 (ultrafiltered) | 0.12 ± 0.06 (total) | |||||||||||
Drinking water | <0.05 (filtered 0.45 μm) | <50 | All in μg L−1 | |||||||||
<0.05 (ultrafiltered) | ||||||||||||
Douglas River drainage system affected by U mining, CA | 7 sampling points over 5 years (1982–1986) | <5.0 (except in the mine effluent and occasionally in a few sampling points) | μg L−1 | <5000 | 1% in HNO3 | unfiltered | AAS | 5000 | ENV | 53 | ||
Great Lakes (surface water): | median values | ppb | 5 mL HNO3 in 1 L sample | 0.5 μm Teflon filter | Particulate digestion: 10% HNO3 and 30% H2O2, 80 °C, 4 h | not given | ENV | 54 | ||||
Lake Huron, 1981 | 0.86 | 860 | 0.079 | |||||||||
Lake Erie, 1981 | 0.69 | 690 | 0.23 | |||||||||
Lake Michigan, 1981 | 0.81 | 810 | 0.020 | |||||||||
Lake Superior, 1983 | 0.13 | 130 | 0.0050 | HG-AAS | ||||||||
Lake Ontario, 1981 | 1.4 | 1400 | 0.34 | |||||||||
Lake Ontario, 1985 | 0.27 | 270 | 0.0078 | |||||||||
All in ppb | ||||||||||||
Tap water, DK | 79 (n = 3) | nM | 16![]() |
not mentioned | not mentioned | Voltammetry with a CME (graphite paste containing 1-(2-pyridylazo-2-naphthol) | 21 | ANAL | 55 | |||
NBS-SRM 1643 b | 51 (n = 4) | 10![]() |
||||||||||
Tap water, Warsaw, PL | 2 samples | 0.19 | μg L−1 | 190 | pH = 1 (HCl) | unfiltered | UV irradiation and reduction with hydrazine | 20 | ANAL | 56 | ||
Vistula River, PL | 6 samples | 0.31 ± 0.03 | 310 | HMDE-DP-ASV | ||||||||
Amazonian waters, BR: | μg L−1 | 5 mL HNO3 in 500 mL sample | 0.2 μm Nucleopore membranes (after acidification) | ICP-MS | not given | ENV | 57 | |||||
Rio Negro | 8 samples | <0.02 (all) | <20 | |||||||||
Rio Solimões | 8 samples | <0.02 (3), 0.05, 0.04, 0.06, 0.2, 0.06 | <20–60 | |||||||||
Shield streams in Carajás | 8 samples | <0.02, <0.04 (6), 0.06 | <20–60 | |||||||||
Spring water, Oodaki town, JP | 0.071 (RSD: 6.30%, n = 4) | ppm | 71![]() |
not mentioned in the English abstract | not mentioned in the English abstract | Co-precipitation with zirconium hydroxide; filtration | 10 | ANAL | 36 | |||
River water, Chiba, Youro valley, JP | 0.012 (RSD: 8.30%, n = 4) | 12![]() |
DP-ASV | |||||||||
Norwegian hard rock groundwater: | 145 samples | median = 0.001 | μg L−1 | 1 | not acidified | unfiltered | ICP-MS | 1 | ENV | 58 | ||
Oslo | 0.001 | Surface water values come from reports | ||||||||||
Bergen | 0.001 | |||||||||||
Norwegian surface waters | 473 samples | median <0.02 | ||||||||||
Finnish surface waters | several hundred samples | median = 0.005 | ||||||||||
Ob River, RU | 17 samples | 0.04 (CV = 0.63) | μg L−1 | 40 | not mentioned | ‘blue ribbon’ paper filter | Voltammetry | 10 | ENV | 59 | ||
Major tributaries Ob River, RU | 12 samples | 0.14 | μg L−1 | 140 | not mentioned | not mentioned | not given | not given | ENV | 60 | ||
Marmato District (Au mining), CO: | not mentioned | not mentioned | Particulate digestion: strong acid (not given) | 2 × 106 | ENV | 61 | ||||||
Marmato district (summer) | 8 samples | <2–30 | ||||||||||
Marmato district (winter) | 4 samples | <2–34 | Analytical technique not given | |||||||||
Cauca River (summer) | 5 samples | <2–2 | ||||||||||
Cauca River (winter) | 6 samples | <2–2 | ||||||||||
All in ppm | ||||||||||||
Alkaline lakes in the Sasykkul depression, East Pamirs, TJ: | ng L−1 | pH 3 (HNO3) | 0.4 μm membrane filter | Co-precipitation: CdS in the presence of FeCl3, filtration (no conditions given), drying, filtration (no conditions given), drying | 0.1 | ENV | 62 | |||||
Tuzkul Lake | 0.7 | 0.7 | ||||||||||
Sasykkul Lake | 2.8 | 2.8 | Emission spectrochemical analysis | |||||||||
Bulunkul Lake (fresh lake), TJ | 1.1 | 1.1 | ||||||||||
56 European bottled mineral waters | median = 0.001 (<0.001–0.024) | μg L−1 | 1 | not acidified | unfiltered | ICP-MS | 1 | ENV | 63 | |||
Lakes in the Kola Peninsula, RU | 120 lakes | <0.02 | μg L−1 | <20 | not acidified | unfiltered | ICP-MS | not given | ENV | 64 | ||
Crystalline bedrock groundwaters, NO | 476 samples | median <0.001 | μg L−1 | <1 | 4 mL conc HNO3 in a 400 mL sample | unfiltered | ICP-MS | 1 | ENV | 65 | ||
max = 3.2 | ||||||||||||
Groundwater Wells El-Menoufia, Nile Delta, EG | 4 samples | 1, 0.2, 0.2, 0.4 | μg L−1 | 1000, 200, 200, 400 | HCl added, pH not given | 0.45 μm cellulose acetate membrane filter | HMDE-DPASV | 38 | ANAL | 66 | ||
River Elbe, DE | 18 samples | 1.05 ± 0.09 μg g−1 | not mentioned | 0.45 μm-Nucleopore filters | Particulate digestion: HNO3/HF high-pressure with microwave induction | not given | ENV | 67 | ||||
TXRF or ICP-AES or ICP-MS or INAA | ||||||||||||
Vicinity of a Cu–W mine, Dalsung mine, KR | 17 samples | <1 | μg L−1 | <1000 | pH < 2 (HCl) | 0.45 μm membrane filter paper | Particulate digestion: fuming HNO3 and Mg(NO3)2 | not given | ENV | 68 | ||
HG-ICP-AES | ||||||||||||
Llobregat River, ES | 93 samples (3 sampling points, Jul 96–Dec 2000) | <0.08 | μg L−1 | <80 | 1% HNO3 (v/v) | unfiltered | ICP-MS | not given | ENV | 69 | ||
Salí River watershed, AR | 110 samples (37 sampling points, 4 sampling campaigns) | <0.08 | μg L−1 | <80 | 1% HNO3 (v/v) | unfiltered | ICP-MS | not given | ENV | 70 | ||
Tap water | 6.2 | ng mL−1 | 6200 | not mentioned | not mentioned | HMDE-ASV using morin as a complexing agent | 4500 | ANAL | 71 | |||
Groundwater in a closed-basin aquitard, La Laguna Region, MX: | mg L−1 | pH < 2 (HNO3) | not mentioned | ICP-AES or ICP-MS | not given | ENV | 72 | |||||
Spring | 1 spring | 0.002 | 2000 | |||||||||
Carbonate aquifer | 6 wells | 0.0002–0.005 | 200–5000 | |||||||||
Thin alluvial fan | 2 wells | 0.002, 0.005 | 2000, 5000 | |||||||||
Aquitard | 6 brine production wells | 0.02–0.04 | 20![]() ![]() |
|||||||||
Lakes, ponds and reservoirs, TW and offshore islands | 50 samples | <3 | ppb | <300 | yes but no details given | 0.45 μm Nalgene filter | ICP-MS | 300 | ENV | 73 | ||
Mouth of the St. Lawrence River, CA | 13 samples | 0.7 ± 0.3 | ng L−1 | 0.7 | 0.29 ± 0.11 μg g−1 | pH 2 (HNO3) | 0.45 μm polycarbonate membrane and polypropylene filters | ICP-MS | not given | ENV | 74 | |
Particulate: filter digestion with 2 mL conc. HNO3 and 1 mL HF | ||||||||||||
Tap water | 0.23 (RSD 5.2%, n = 5) | μg L−1 | 230 | not mentioned | not mentioned | CPE-ASV using BPR as complexing agent | 104 | ANAL | 75 | |||
River water 1 | 0.42 (RSD 3.9%, n = 5) | 420 | ||||||||||
River water 2 | 0.67 (RSD 2.8%, n = 5) | 670 | ||||||||||
Lake Van, TR | 10 locations (each n = 3) | 63.1 ± 43.1 (14–110) | ppb | 63![]() |
0.02 M HNO3 | blue-band paper filter | Bi-DEDTC complex sorbed onto activated C | not given | ENV | 76 | ||
Rivers flowing into Lake Van, TR | 5 rivers (each n = 3) | 45.2 ± 35.8 (7–96) | 45![]() |
FAAS | ||||||||
River water (no details given) | 5 samples | 1.19, 0.74, 0.43, 0.39, 0.00 | ng mL−1 | 1190, 740, 430, 390, 0 | not mentioned | not mentioned | SPE: XAD-4-salen; filtration Whatman # 2 | not given | ANAL | 77 | ||
GF-AAS | ||||||||||||
Tap water, Arak, IR | 0.160 ± 0.01 (n = 3) | ng mL−1 | 160 | pH 3.0–3.5 (dil. H2SO4) | 0.45 μm filter | Cloud point extraction (surfactant: Triton X-114, complexing agent: ditizone) | 20 | ANAL | 78 | |||
ET-AAS | ||||||||||||
River water certified reference material (JSAC 0301-1) | 0.000053 ± 0.000009 (n = 5) | μg L−1 | 0.053 | — | not mentioned | Preconcentration: chelating resin (Chelex 100) | 0.01 | ANAL | 79 | |||
High efficiency nebulization ICP-MS | ||||||||||||
High blank value | ||||||||||||
Tap water, Arak University, Arak, IR | 3.5 ± 1.2 | ng mL−1 | 3500 | not mentioned | not mentioned | HMDE-ASV stripping using TPN as complexing agent | 800 | ANAL | 80 | |||
Duero Cenozoic basin, ES (As-rich groundwater) | 514 water samples (groundwater and springs) | BDL–0.05 | μg L−1 | BDL–50 | not mentioned | not mentioned | ICP-MS | not given | ENV | 81 | ||
Nainital, IN: | 18 locations | ppb | not mentioned | not mentioned | Co-precipitant and internal standard: PdCl2, precipitant: NaDDTC; filtration 0.4 μm, precipitant: NaDDTC; filtration 0.4 μm | not given | ENV | 82 | ||||
Lake water | 2.6 ± 0.5 | 2600 | ||||||||||
Tap water | 1.51 | 1510 | ||||||||||
Spring water | 2.31 | 2310 | EDXRF | |||||||||
Pearl River Delta Economic Zone, CN: | ppb | not mentioned | “upper part of the clean water in the sample bottle” analysed | ICP-MS | not given | ENV | 83 | |||||
West River | 4 samples | 0.002–0.003 | 2–3 | |||||||||
East River | 9 samples | 0.001–0.024 | 1–24 | |||||||||
Pearl River Delta | 14 samples | 0.001–0.032 | 1–32 | |||||||||
North River | 1 sample | 0.018 | 18 | |||||||||
Shenzen River | 1 sample | 0.039 | 39 | |||||||||
Tirupati, IN: | μg L−1 | 5 mL HNO3 in 1 L | 0.45 μm cellulose membrane filter (after acidification) | SPE: piperidene dithiocarbamate-coated Amberlite XAD-7 resin | 1200 | ANAL | 47 | |||||
“Natural” water 1 | 2.0 ± 0.04 (n = 5) | 2000 | ||||||||||
“Natural” water 2 | 1.7 ± 0.08 (n = 5) | 1700 | ICP-MS | |||||||||
Allard River, CA | 3 sites | 0.01, 0.01, 0.01 | nmol L−1 | 2, 2, 2 | “several drops of conc. HNO3” | 0.45 μm filter cartridges | ICP-MS | 2 | ENV | 84 | ||
Colombière River, CA | 3 sites | 0.01, 0.01, 0.02 | 2, 2, 4 | |||||||||
Tap water | BDL | ng mL−1 | not mentioned | filtration mentioned (conditions not given) | HMDE-ASV using chromazorul-S as complexing agent + CWT | 100 | ANAL | 85 | ||||
River water | 0.3 | 300 | ||||||||||
Takahashi River, Okayama, JP | 2.08 ± 0.05 (n = 5) | pg mL−1 | 2.08 | not mentioned | not mentioned | Preconcentration: glycine-type chitosan resin | 0.1 | ANAL | 48 | |||
ICP-MS | ||||||||||||
Xuzhou, CN: | μg L−1 | 2% (v/v) HNO3 | 0.45 μm filter | Preconcentration: retention of Bi complex with Bismuthiol I on a nylon fibre-packed microcolumn | 2.8 | ANAL | 86 | |||||
River water | 0.53 ± 0.03 (n = 5) | 530 | ||||||||||
Lake water | 0.34 ± 0.02 (n = 5) | 340 | ||||||||||
Tap water | 0.26 ± 0.02 (n = 5) | 260 | HG-AFS | |||||||||
Tap water 1 | 33.8 ± 9.8 (n = 4) | μg L−1 | 33![]() |
not mentioned | not mentioned | Cloud point extraction (surfactant: Tween 80) | 800 | ANAL | 87 | |||
Tap water 2 | 34.9 ± 8.6 (n = 4) | 34![]() |
||||||||||
Mineral water 1 | 264 ± 43 (n = 4) | 264![]() |
||||||||||
Mineral water 2 | 211 ± 19 (n = 4) | 211![]() |
FAAS | |||||||||
Mineral water 3 | 235 ± 15 (n = 4) | 235![]() |
||||||||||
Surface water, Yangzhong city, CN | 28 samples | 0.043 ± 0.180 (0.001–0.963) | μg L−1 | 43 | pH < 1 | 0.46 μm filter | HR-ICP-MS | not given | ENV | 88 |
System | Bi concentration | Source given | Ref. |
---|---|---|---|
Seawater | 0.00002 mg L−1 | none | 89,90 |
Seawater | 0.02 μg L−1 | 91 | 92 |
Seawater | 1 × 10−10 M = 2 × 10−2 μg L−1 | 13 | 93 |
Seawater | 0.02 μg L−1 | none | 94 |
Seawater | 4 × 10−5 ppb | Lee, personal communication | 95 |
Surface seawater | ≈0.2 pmol kg−1 | 22 | 96 |
Surface observed concentrations in seawater | 20 ng kg−1 | 13 | 97 |
Predicted mean water concentration | 10 ng kg−1 | 13 | 97 |
Vertex IV, Hawaii | Profile: 11 values; 36 pg kg−1 (surface) | 22, 28 | 98 |
Surface waters Atlantic | 0.25 pM | 22 | 99 |
Surface waters Pacific | 0.2 pM | 26 | 99 |
Deep waters Pacific | 0.02 pM | 26 | 99 |
Deep-Pacific Ocean | 2 × 10−14 mol kg−1 | 28 | 100 |
Seawater | 0.0042 × 10−12 g g−1 | 99 | 101 |
Seawater | 0.2 to 0.1 pmol L−1 up to 1000 m, 0.015 pmol L−1 at 3000 m depth | 28,96 | 102 |
Seawater | 4 × 10−9 ppm | 101 | 103 |
Seawater | 2 × 10−8 mg L−1 | none | 104 |
Seawater | 1.6 × 10−15 mol L−1 | probably 105 | 106 |
Seawater | 20 ng L−1 | 107 | 108 |
Seawater | 400 ptt | none | 109 |
North Pacific Ocean | 0.03 ng kg−1 | 28 | 110 |
Ocean | 0.05 μmol m−3 | 97 | 111 |
North Pacific Ocean | 0.03 ng kg−1 | 111 | 113 |
Surface ocean water | 20–40 ng L−1 | 90 | 113 |
World ocean water | 20 ng L−1 | 112 | 113 |
DLa in ng L−1 | Methodb | Applicationc | Ref. |
---|---|---|---|
a When the value in the original publication is not in ng L−1, the original value and units are also given in brackets. b See corresponding list for meaning of abbreviations. c BDL = below detection limit. | |||
200![]() |
β-correction spectrometry | Spiked river water | 115 |
80 (0.08 ng mL−1) | FI-HG-ICP-TOFMS | NIST 1643d: 14.26 μg L−1 | 116 |
8500 (8.5 μg L−1) | ETAAS with tungsten containing chemical modifiers | Spiked seawater; natural seawater: BDL | 117 |
95![]() |
Optical sensor based on (2E,4E)-5-(2,4-dinitrophenyl amino)penta-2,4-dienal | Seawater, tap water, mineral water, river water: BDL | 118 |
1800 (1.8 μg L−1) | Co-precipitation with Cu(II)-9-phenyl-3-fluorone + ICP-MS | Lake water, two different tap waters: BDL | 119 |
800 (0.8 ng mL−1) | ASV (HMDE) using TPN as complexing agent | Tap water: see Table 2 | 80 |
800 (0.8 μg L−1) | Cloud point extraction (surfactant: Tween 80) + FAAS | Tap and mineral water: see Table 2 | 87 |
2.7 (0.0027 ng mL−1) | Trapping on resistively heated W coil + HG-AAS | Certified reference water: TMDW: 10.3 μg L−1 | 120 |
25 | HG, sequestration in graphite tubes, AAS | Brackish water: BDL | 121 |
1200 (1.2 ng mL−1) | ASV using fast red as complexing agent | Spiked samples; unspiked spring and tap water: BDL | 122 |
104 (5 × 10−10 mol L−1) | ASV (CPE) using BPR as complexing agent | Tap and river water: see Table 2 | 75 |
4500 (4.5 ng mL−1) | ASV (HMDE) using morin as complexing agent | Tap water: see Table 2 | 71 |
1200 (1.2 μg L−1) | Fluorimetry of the complex formed by BiI4− and crystal violet | Potable water: BDL | 123 |
100 (0.10 ng mL−1) | ASV (HMDE) using chromazorul-S as complexing agent + CWT | Tap water: BDL; river water: 0.3 ng mL−1 | 85 |
not given | SPE: XAD-4-salen + GF-AAS | River water: see Table 2 | 77 |
167 (8 × 10−10 mol L−1) | Complexation with thiourea and Br− in acidic media + retention on activated C + spectrophotometry | Only spiked samples because “tested water samples were found to be free from Bi content” | 124 |
70 | HG-ETAAS with U-treated graphite tube | Seawater: see Table 1 | 43 |
0.1 (0.1 pg mL−1) | Absorption on glycine-type chitosan resin + ICP-MS | Seawater and freshwater: see Tables 1 and 2 | 48 |
0.06 | Comparison of FI-ICP-MS and FI-ETV-ICP-MS | NRCC CASS-3 and NASS-4: BDL | 125 |
900 and 1200 (0.9 and 1.2 μg L−1) | SPE: sodium DEDTC or piperidene dithiocarbamate-coated Amberlite XAD-7 resin + ICP-MS | “Natural” and seawater: see Tables 1 and 2 | 47 |
900 (0.9 ng mL−1) | On-line preconcentration: chitosan resin functionalized with CCTS-DHBA + ICP-AES | NRCC SLRS-4 and CASS-4, river and seawater: BDL | 49 |
Off-line: see Table 2 | |||
20 (0.02 ng mL−1) | Cloud point extraction (surfactant: Triton X-114, complexing agent: ditizone) + ET-AAS | Tap water: see Table 2 | 78 |
140 (0.14 ng mL−1) | SPE: amberlite XAD-2 modified with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol + DP-ASV | Only spiked samples because “no bismuth was present in these samples” | 126 |
500 (0.5 μg L−1) | SPE: silica gel modified with 3-aminopropyltriethoxysilane + GF-AAS | Seawater: see Table 1 | 44 |
800 (0.8 μg L−1) | SPE: Chromosorb-107 with and without APDC + GF-AAS | CRM-SW: BDL; seawater: see Table 1 | 45 |
31.0 ng L−1 | Preconcentration: sorption onto 8-hydroxyquinoline immobilized polyacrylonitrile hollow fibre membrane + ICP-MS | Seawater: see Table 1 (they measure values lower than the DL) | 41 |
2.8 ng L−1 | Preconcentration: retention of Bi complex with Bismuthiol I on a nylon fibre-packed microcolumn + HG-AAS | Freshwater: see Table 2 | 86 |
2 (0.002 μg L−1) | Tandem preconcentration by chelating resin adsorption (Chelex 100) and La co-precipitation + ICP-MS | NASS-4 open seawater, Ise Bay: BDL | 42 |
0.03 (0.00003 μg L−1) | Preconcentration by chelating resin adsorption (Chelex 100) + ICP-MS | NASS-4 open seawater: BDL; Ise Bay: see Table 1 (less than 50% recovery) | 42 |
10 (0.01 ng mL−1) | Octadecyl bonded silica cartridge modified with cyanex 301 + GF-AAS | Only spiked samples | 127 |
0.05 (0.00005 μg L−1) | Tandem preconcentration using a chelating resin (Chelex 100) + ICP-MS | CASS-4 seawater: BDL; Ise Bay: see Table 1 | 46 |
The actual speciation of bismuth in natural waters does not seem to be well established. To illustrate this point, Table 5 gathers information published on bismuth speciation in seawater. All these results are, in principle, based on thermodynamic calculations but the constants used for these calculations are rarely given and their validity does not seem to have ever been systematically evaluated. On the contrary, Table 5 shows that most of the authors simply copy statements from previous publications that, in turn, cite previous ones. When the thread is tracked back to the initial sources, there appear to be very few of them and, at least in one case, the original is an old publication in Russian which most of the authors are unlikely to have read. After a long search, I have had access to the original publication (original text translated as a footnote in Table 5) and, amazingly, the set of suggested species does not seem to be based on any thermodynamic calculation. Moreover, it even contains an error in one species (BiCl−) that was reproduced in a well-known reference work130 and, again, in a very recent book.113 As mentioned for total concentration values, superseded distributions remain in the literature without any apparent scientific reason.
Species | Source given | Ref. |
---|---|---|
a Because of the difficulties in accessing the original source, the translation of the original text is given: “Bismuth. According to the data of I. and W. Noddack,12 in the water of the Gullmar Fjord the concentration of Bi is 2 × 10−8%. This is the only determination of Bi in sea water. Soluble salts are BiO1+ (perhaps BiOCl, BiCl1−) and the most insoluble salt is BiOCl”.) and the most insoluble salt is BiOCl”. b Question mark in the original publication. | ||
soluble: BiO+ (perhaps BiOCl, BiCl−), insoluble: BiOCla | no reference | 129 |
BiO+, BiCl−, BiOCl, BiOCl | 129 | 130 |
BiO+, Bi(OH)2+ | no reference | 93 |
BiO+, Bi(OH)2+, Bi6(OH)126+?b | 129, cited in 130 | 131 |
BiO+, Bi(OH)2+ | no reference | 132 |
100% complexed to OH (no species given) | original calculation (no equilibrium constant values given) | 105 |
BiO+, Bi(OH)2+ | 105,132 | 96 |
Bi(OH)30 | 133 | 101 |
BiO+, Bi(OH)2+ | no reference | 104 |
Bi(OH)30 | 134 | 135 |
BiO+, Bi(OH)2+ | 96 | 135 |
BiO+, Bi(OH)2+ | 96 | 136 |
Bi(OH)30 | no reference | 106 |
BiCl4− | 137 | 108 |
Bi(OH)2+, Bi(OH)30, Bi(OH)4− | original calculation (pKs = 4.86, 12.7) | 138 |
Bi(OH)30 | no reference | 139 |
BiO+, Bi(OH)2+, Bi(OH)30 | no reference | 140 |
BiO+, Bi(OH)2+ | 96 | 141 |
BiO+, BiCl−, BiOCl, BiOCl | 131 | 113 |
The situation is no better when so-called heterogeneous complexants (e.g., natural organic matter, metal oxides, aluminosilicates) are considered. To our knowledge, no laboratory study exists where complexation/sorption of bismuth by these complexants has been quantified. Dzombak and Morel, in their classic book on surface complexation modelling of hydrous ferric oxide binding,142 did not mention any binding value for bismuth. Nor did they venture to estimate it from LFER's (Linear Free Energy Regression) as they did for other elements for which experimental data were also missing (e.g., antimony, molybdenum, selenium). However, there are many reasons to think that bismuth binding by heterogeneous complexants is far from negligible, namely: (i) significant amounts of bismuth have been found associated to ‘particulate’ phases in natural waters (Tables 1 and 2); (ii) the few seawater profiles measured to date22,28 clearly show non-conservative behaviour, with removal in upper waters and regeneration from suspended particles to solution roughly associated with the oxygen minimum at 500, attributed by the authors to the dissolution of manganese oxides acting as a carrier phase; (iii) according to Pearson's HSAB (Hard Soft Acid-Base) theory, Bi(III) should be a broad-line or soft metal ion; (iv) in the frame of its medical applications, bismuth complexation by biomolecules such as metallothioneins and transferrin has been studied in detail,143–145 and strong binding found. Finally, other applications point to significant complexation of Bi(III) by organic ligands, for instance the fact that the antibacterial properties of bismuth are greatly improved when bismuth is combined with certain lipophilic thiol compounds146 which enhance not only the lipophilicity but also the solubility of bismuth, or the extended use of a parameter called BiAS (bismuth active substances) to measure the presence of non-ionic surfactants present in polluted waters.147
Knowledge about methylated species of bismuth in environmental and biological media is very limited. In contrast to arsenic and antimony, no methylated bismuth species have ever been found in surface waters.148
AAS | atomic absorption spectrometry |
AES | atomic emission spectrometry |
AFS | atomic fluorescence spectrometry |
APDC | ammonium pyrolidine dithiocarbamate |
ASV | anodic stripping voltammetry |
BDL | below detection limit |
BPR | bromopyrogallol red |
CCTS | cross linked chitosan |
CFF | cross flow filtration |
CL | 95% confidence limits |
CME | chemically modified electrode |
CPE | carbon paste electrode |
CV | coefficient of variation |
CWT | continuous wavelet transform |
DEDTC | diethyldithiocarbamate |
DHBA | 3,4-dihydroxy benzoic acid |
DCASV | direct current ASV |
DL | detection limit |
DPASV | differential pulse ASV |
EDXRF | energy dispersive X-ray fluorescence |
ETAAS | electrothermal AAS |
ETV | electrothermal vaporization |
FI | flow injection |
F2H2Dz | 1,2-di-(2-fluorophenyl)-3-mercaptoformazan |
FAAS | flame atomic absorption spectrometry |
FIA | flow injection analysis |
GF | graphite furnace |
GFAAS | graphite furnace AAS |
HG | hydride generation |
HMDE | hanging mercury drop electrode |
HR | high resolution |
ICP | inductively coupled plasma |
INAA | instrumental neutron activation analysis |
MCGE | mercury-coated graphite electrode |
MS | mass spectrometry |
N | number of samples |
NaDDTC | sodium diethydithiocarbamate |
PSA | potentiometric stripping analysis |
RDE | rotating disc electrode |
RRDE | rotating ring-disc electrode |
RSD | relative standard deviation |
salen | N,N′′-bis(salicylidene)ethylenediamine |
SFC | supercritical fluid chromatography |
SPE | solid-phase extraction |
SPM | solid suspended matter |
SW-ASV | square wave ASV |
TOFMS | time-of-flight mass spectrometry |
TPN | thymolphthalexone |
TXRF | total X-ray fluorescence spectrometry |
UV | ultraviolet |
VG | vapor generation |
Footnote |
† Part of a themed issue dealing with water and water related issues. |
This journal is © The Royal Society of Chemistry 2010 |