Dissolved organic carbon concentrations and fluxes along the Moisie River, Quebec

SUMMARY. 1. The main stream and tributaries of a 145 km reach of the Moisie River, Quebec, were examined for temperature, conductivity, pH, dissolved organic carbon (DOC),%DOC>100,000 nominal molecular weight (NMW), optical density (OD₃₅₀), and the ratio of OD₄₀₀ to OD₆₀₀ (E4:E6).
2. Dissolved organic carbon concentrations correlated closely with OD₃₅₀ ( r ²=0.92, P <0.001). However,%DOC>100,000 NMW did not correlate with the E4:E6 ratio.
3. Except for a slight increase in%DOC> 100,000 NMW ( r ²=0.37, P <0.05), no change in any characteristic occurred down the length of the Moisie River, despite consistently higher levels of DOC in the tributaries.
4. Results suggest that high concentrations of DOC in tributary waters are rapidly removed within the main river channel. These results are discussed in terms of both biotic and abiotic models of in-strcam processing.     

Seasonal changes in the concentration and colour of humic substances in some aquatic environments

SUMMARY. 1. Between February and September 1974, concentrations of fulvic and humic acids in waters from a cryoboreal region of the Precambrian Shield in Quebec varied between 0.5–6.1 mg 1⁻¹ and 0.1–6.5 mg 1⁻¹ respectively. Whereas the fulvic acids usually remained relatively constant during this period, humic acids showed appreciable increases.
2. The number and weight average molecular weights of the fulvic acids (∼5000 and ∼22,000 daltons respectively) were lower than those of the humic acids (∼20,000 and ∼75,000 daltons respectively). The average molecular weight of the aquatic humic matter often decreased during late summer and early autumn. During spring floods the molecular weight of fulvic acids increased and that of humic acids declined.
3. Because the aquatic humic acids were more intensely coloured than fulvic acids, they contributed more than 30% of the colour of the water even though they accounted for only 15% of the concentration of humic matter. The colour intensity of both fulvic and humic acids generally appeared to increase during the latter part of the summer, when there was normally a decrease in the value of the colour quotient (E₄/E₆ ratio), indicating the accumulation in the waters of more humified material.     

Immobilization of dissolved organic matter from groundwater discharging through the stream bed

SUMMARY. 1. In laboratory experiments, 9.7–25.7% of dissolved organic carbon (DOC) in groundwater (at concentrations of 18.7–24.8 mg 1-⁻¹) was immobilized after perfusion through 8-cm-deep (22-cm-diameter) cores of stony stream-bed substratum.
2. This represented immobilization rates of 7.1–23.5 mg m⁻² h⁻¹ or, extrapolated across the year, potential immobilization rates within the stream bed of 62.2–205.9g m⁻² yr⁻¹. Actual rates in the entire stream bed were probably higher because perfusion through the experimental cores did not reduce groundwater DOC concentrations to levels measured in the adjacent stream.
3. Natural concentrations of dissolved free amino acids (DFAAs) in groundwater were generally unchanged following perfusion through the cores, suggesting the maintenance of a dynamic equilibrium in their concentrations.
4. Selective enrichments of amino acids in groundwater (up to 20-fold) were entirely immobilized following perfusion, indicating their rapid retention and flux in this environment. Thus, immobilization of the bulk DOC in stream-bed cores probably did not reflect net reductions in dissolved free, low-molecular-weight material, with higher molecular weight, more 'refractory' material being immobilized instead.
5. We conclude that groundwater can contribute substantial amounts of DOC, both high and low molecular weight, to a stream ecosystem. The stream bed is the site at which much of this material could be initially immobilized and made available to the stream trophic structure.     

Phosphorus transformations in the epilimnion of humic lakes: abiotic interactions between dissolved humic materials and phosphate

SUMMARY. 1. Sephadex gel filtration of filtered water from small, Finnish forest lakes demonstrated abiotic movement of ³³P from added PO₄ to two higher molecular weight fractions. This movement was most pronounced in waters with high humic content which also had high iron content. The two fractions which took up ¹³P had nominal molecular weights of > 100,000 and 10,000-20,000.
2. An equilibrium existed between free PO₄ and the two fractions. However, one fraction, at least, appeared to exist in two phases, with one phase in rapid equilibrium with free PO₄ but the other in only slow equilibrium.
3. Additions of ferric iron up to 1 mg Fe l⁻¹ to the filtered lake water stimulated movement from free PO₄, provided high concentrations of humic materials were present. In the absence of humic materials even 0.1 mg Fe 1⁻¹ would precipitate all added ³³PO₄.
4. The high molecular weight P was only partially reactive with standard molybdate reagents. Exposure of the high molecular weight P to sunlight caused a small release of PO₄ under the experimental conditions employed.
5. Possible implications for biological phosphorus demand of such sequestration of free PO₄ by humic materials in combination with iron are discussed.     

Chemical Characteristics of Particulate, Colloidal, and Dissolved Organic Material in Loch Vale Watershed, Rocky Mountain National Park

The chemical relationships among particulate and colloidal organicmaterial and dissolved fulvic acid were examined in an alpine andsubalpine lake and two streams in Loch Vale Watershed, Rocky MountainNational Park. The alpine lake, Sky Pond, had the lowest dissolved organiccarbon (DOC) (0.37 mgC/L), the highest particulate carbon (POC) (0.13mgC/L), and high algal biomass. The watershed of Sky Pond is primarilytalus slope, and DOC and POC may be autochthonous. Both Andrews Creekand Icy Brook gain DOC as they flow through wet sedge meadows. Thesubalpine lake, The Loch, receives additional organic material from thesurrounding forest and had a higher DOC (0.66 mgC/L). Elemental analysis,stable carbon isotopic compositon, and ¹³C-NMR characterizationshowed that: 1) particulate material had relatively high inorganic contentsand was heterogeneous in compositon, 2) colloidal material was primarilycarbohydrate material with a low inorganic content at all sites; and 3)dissolved fulvic acid varied in compositon among sites. The lowconcentration and carbohydrate-rich character of the colloidal materialsuggests that this fraction is labile to microbial degradation and may beturning over more rapidly than particulate fractions or dissolved fulvic acid.Fulvic acid from Andrews Creek had the lowest N content and aromaticity,whereas Sky Pond fulvic acid had a higher N content and lower aromaticitythan fulvic acid from The Loch. The UV-visible spectra of the fulvic acidsdemonstrate that variation in characteristics with sources of organic carboncan explain to some extent the observed non-linear relationship betweenUV-B extinction coefficients and DOC concentrations in lakes.     

Terrestrial export of highly bioavailable carbon from small boreal catchments in spring floods

1. We assessed the terrestrial export of organic carbon, which effectively supported aquatic bacterial production (BP), from small boreal catchments during spring flood. We analysed stream runoff from nine small catchments with different proportions of peat mires and coniferous forests by monitoring the dissolved organic carbon (DOC) flux in combination with conducting bacterial bioassays.
2. Multiple linear regression analysis showed that BP during 7-day-dark bioassays (BP₇; μg C L⁻¹day⁻¹) was explained by both the quantity and quality (low-molecular weight fractions) of the DOC. BP₇ can be used as a measure of export of terrestrial organic carbon that is highly bioavailable.
3. Total export of DOC during spring flood from the different catchments ranged from 20 to 27 kg ha⁻¹ and was negatively correlated to forest cover (%). However, the export of BP₇ carbon was positively correlated to forest cover and varied from about 0.1 kg ha⁻¹ in mire-dominated streams to about 0.2 kg ha⁻¹ in forest-dominated streams.
4. The high bioavailability of forest carbon suggests that forests are the main contributors of BP-supporting carbon in boreal streams although mires have higher area-specific export of DOC.     

Chromatographic techniques for the separation of Al and associated organic ligands present in soil solution

Organic acids including humic, fulvic, aliphatic and aromatic acids comprise part of the dissolved organic carbon (DOC) present in soil solution. They act as ligands for trace metals and are effective detoxifiers of monomeric aluminium (Al). Solid phase extraction (SPE) techniques permit fractionation of the DOC into organic classes but yield no information on the pre-existing Al/organic acid complexes. Aliphatic and aromatic acids may be separated and determined by High Performance Liquid Chromatography (HPLC); however, the conditions used dissociate the organic acid Al complexes. Humic and fulvic acids are of a variable and ill-defined nature and only limited information exists regarding their binding of Al. This paper reports on fractionation studies of soil solutions, using both SPE and molecular weight cut-off filters, to characterise the DOC components and on the subsequent development of a size exclusion chromatography (SEC) system for the separation of organically complexed Al into different species using a low ionic strength mobile phase at pH 4.2. Model complexes of Al and Cu citrate were used to evaluate chromatographic performance of a Fractogel TSK HW-40(S) column (1×30 cm). For soil solution samples, the column eluate, after passing through a UV detector, was directly coupled to an Inductively Coupled Plasma Atomic Emission Spectrometer (ICPAES) for on-line multi-element detection to characterise DOC and trace metal distribution.Fractionation studies revealed that polysaccharides constituted the major proportion of the DOC which passed the 10000 dalton molecular weight cut-off filter. Analysis of soil solutions from an organically amended soil by the SEC-ICPAES system showed that Al, Fe and Mn eluted as multiple peaks prior to the bed volume, indicating their presence as complexes with organic ligands.     

Effect of pH on molecular weight and size of fulvic acids in drainage water from peaty grassland in NW Netherlands

Summary The effect of pH on the molecular weight and size of fulvic acids (FA) in a peaty ditch water was studied by dialysis, Sephadex G-25 gel filtration and ultrafiltration. The results of these techniques of fractionating according to particle size indicated that the molecular weight and size of FA decrease with decreasing pH. The ratio of the light absorbances at 250 and 365 nm (E2/E3) of ditch water increased with decreasing pH corresponding with the results of dialysis, gel filtration and ultrafiltration of FA.Our results do not correspond with the ideas of the macromolecular structure of soil FA as developed by Schnitzer¹⁶.     

Microbial activity associated with seston in headwater streams: effects of nitrogen, phosphorus and temperature

SUMMARY 1. The influences of temperature and dissolved nitrates and phosphates on microbial activity associated with suspended fine particulate organic matter (seston) were evaluated in four headwater streams in the southern Appalachian Mountains.
2. Temperature manipulations of ± 5°C always induced significant changes in [¹⁴C] glucose mineralization (ANOVA; P <0.05) and [³H]thymidine incorporation (ANOVA; P <0.05).
3. Nutrient amendments of 1.0 mg NO₃ I⁻¹ and 0.05 mg PO₄I⁻¹ induced no significant alterations in bacterial mineralization of [¹⁴C]glucose (ANOVA; P >0.05) or incorporation of [³H]thymidine (ANOVA; P >0.05) in short-term (i.e. 3 h) experiments.
4. Microorganisms attached to refractory particulate organic matter do not appear to be limited by nitrogen or phosphorus even in streams with ambient nutrient concentrations as low as 0.06 mg NO₃ I⁻¹ and <0.03 mg PO₄ I⁻¹.
5. Our results indicate that variations in water temperature resulting from diurnal and seasonal temperature fluctuations, forest clear-cutting, and catchment elevation and aspect can have marked effects upon microbial activity and production, while short-term alterations in nutrient regime appear to have no significant effect on microbial activity associated with seston.     

Distribution of dissolved organic carbon and dissolved fulvic acid in mesotrophic Lake Biwa, Japan

The dissolved organic carbon (DOC) concentrations in mesotrophic Lake Biwa were determined by a total organic carbon (TOC) analyzer, and DOC molecular size distributions were determined by size exclusion chromatography (SEC) using a fluorescence detector at excitation/emission (Ex/Em) levels of 300/425 nm with the eluent at pH 9.7. The fluorescence wavelengths for detection were chosen from the result of excitation–emission matrix spectrometry (EEM) analysis for dissolved fulvic acid (DFA) extracted from Ado River (peak A, Ex/Em = 260–270/430–440 nm; peak B, Ex/Em = 300–310/420–430 nm). Ado River DFA was eluted with a retention time (RT) of 7.4–8.9 min and the apparent molecular weight was estimated at 22–87 kDa based on the elution curve for the spherical protein molecular weight standard. A DFA peak eluted at the same retention time as Ado River DFA also appeared in all the samples of Lake Biwa water. From the linear relationship between the peak areas with an RT of 7.4–8.9 min by SEC analysis and DOC values of DFA by TOC analysis of a series of DFA samples (r² = 0.9995), the concentrations of DFA in the lake water were roughly calculated. DFA was distributed within the range 0.25–0.43 mg C l⁻¹ and accounted for 15%–41% of DOC, with the highest ratios observed at a depth of 70 m in August and the lowest at 2.5 m in May.     

Importance of dissolved organic matter produced by duckweed (Lemna minor) in a southern English river

SUMMARY. 1. The quantity of dissolved organic carbon (DOC) released by axenic Lemna minor cultures in the laboratory has been determined by an absolute method and by ¹⁴C labelling.
2. Good agreement was obtained between the two methods and from 1.1% to 2.6% of the total carbon fixed was released.
3. The DOC produced by L. minor has been analysed by ultrafiltra- tion and compared with a similar analysis of DOC in natural river water.
4. The results of ullrafiltration analyses indicate that the proportion of low molecular weight (<1000 Daltons) material in DOM produced by axenic L. minor is significantly greater than is found in its natural habitat.     

Effects of CO2 enrichment on mineral accumulation and nitrogen relations in a submersed macrophyte

1. Six- to eight-week greenhouse experiments with independent control of pH and dissolved CO₂ evaluated the potential for CO₂ enrichment to stimulate the accumulation of Al, Fe, P and N in shoots of Vallisneria americana , particularly at pH 5. These minerals were provided only as they occurred in natural lake sediments.
2. The effect of CO₂ enrichment at pH 5 v pH 7.3 on growth and tissue N concentration was also determined.
3. CO₂ enrichment at pH 5 effected 5.5- and 7-fold increases in total shoot accumulation of Al and Fe, respectively. In a two-way factorial experiment, CO₂ enrichment yielded 6- to 11-fold greater total shoot P accumulation in plants grown on less and more fertile sediments, respectively.
4. In a three-way factorial experiment, CO₂ enrichment stimulated Vallisneria growth, especially at pH 5, and resulted in a 31–58% reduction in tissue [N] for different pH × sediment combinations. These are greater reductions than previously reported. It also increased total shoot N accumulation up to 6-fold, and there were significant interactions with pH and sediment source: the CO₂ enrichment effect on shoot N accumulation was greater at pH 5 than at pH 7.3, and it was greater with the more fertile sediment at pH 5.
5. Water chemistry (pH and/or [CO₂]) and sediment fertility thus both indirectly influenced the accumulation of sediment-derived minerals in macrophyte shoots within the water column.     

Effects of CO2 enrichment on mineral accumulation and nitrogen relations in a submersed macrophyte

1. Six- to eight-week greenhouse experiments with independent control of pH and dissolved CO₂ evaluated the potential for CO₂ enrichment to stimulate the accumulation of Al, Fe, P and N in shoots of Vallisneria americana , particularly at pH 5. These minerals were provided only as they occurred in natural lake sediments.
2. The effect of CO₂ enrichment at pH 5 v pH 7.3 on growth and tissue N concentration was also determined.
3. CO₂ enrichment at pH 5 effected 5.5- and 7-fold increases in total shoot accumulation of Al and Fe, respectively. In a two-way factorial experiment, CO₂ enrichment yielded 6- to 11-fold greater total shoot P accumulation in plants grown on less and more fertile sediments, respectively.
4. In a three-way factorial experiment, CO₂ enrichment stimulated Vallisneria growth, especially at pH 5, and resulted in a 31–58% reduction in tissue [N] for different pH × sediment combinations. These are greater reductions than previously reported. It also increased total shoot N accumulation up to 6-fold, and there were significant interactions with pH and sediment source: the CO₂ enrichment effect on shoot N accumulation was greater at pH 5 than at pH 7.3, and it was greater with the more fertile sediment at pH 5.
5. Water chemistry (pH and/or [CO₂]) and sediment fertility thus both indirectly influenced the accumulation of sediment-derived minerals in macrophyte shoots within the water column.     

Effects of enhanced ultraviolet-B radiation on the production of lipid, polysaccharide and protein in three freshwater algal species

1. The effects of ultraviolet-B (UVB-enhanced) radiation on the production of photosynthates (lipid, protein, polysaccharide and low molecular weight compounds) was examined for three species of algae. Cryptomonas sp., Nitzschia palea and Synechococcus elongatus were selected as representatives of the Cryptophyceae, Bacilliarophyceae and Cyanobacteria, respectively.
2. Laboratory experiments were performed at several UVB_weighted dose rates ranging from 0.018 to 0.391 mW cm^–2. These dose rates span the range of dose rates used in other studies.
3. Effects on the overall photosynthetic rate were observed, even at relatively low UVB_weighted dose rates (0.047 mW cm^–2).
4. The effect of UVB radiation on the fixation of carbon into the main macromolecular pools differed, depending not only on the dosage but on the species examined. However, the observed inhibitory effects were generally non-stochastic. In addition, within each species there were differences in the apparent sensitivity of the various fractions to inhibition by UVB radiation.
5. These results suggest that exposure to UVB radiation has the potential to alter the relative allocation of recently fixed carbon to lipid, protein, polysaccharide and low molecular weight compounds in algae in a species-specific manner.     

Seasonal changes in the character and nitrogen content of dissolved organic matter in an alpine/subalpine headwater catchment

We are studying the chemical quality of dissolved organic nitrogen (DON) in a high-elevation watershed in the Colorado Front Range. Samples were collected over the 2000 snowmelt runoff season at two sites across an alpine/subalpine ecotone to understand how the transition between the lightly vegetated alpine and forested reaches of the catchment influences the chemical character of DON. Samples were analyzed approximately weekly for dissolved organic material (DOM) content and chemical character. A subset of samples was analyzed for the elemental content of fulvic and hydrophilic acids. Concentrations of DON at both sites were highest in the spring at the initiation of snowmelt, decreased during snowmelt, and increased again during the late summer and fall. In contrast, concentrations of dissolved organic carbon (DOC) peaked on the ascending limb of the hydrograph and declined to seasonal minima on the descending limb of the hydrograph. The ratio of DOC:DON showed a seasonal shift at both sites with high values (40 to 55) during peak runoff in early summer and lower values (15 to 25) during low flows late in the runoff season. These results indicate that there was a seasonal change in the relative N content of DOM at both sites. Chemical fractionation of DOC showed that there were temporal and longitudinal changes in the chemical character of DOC. At the alpine site, the fulvic acid content of DOC decreased from 57% in June to 35% in September. The change in fulvic acid was less pronounced at the forested site, from 66% in June to 54% in September. Elemental analysis of fulvic and hydrophilic acids indicated that hydrophilic acids were N rich compared to fulvic acids. Additionally, fulvic and hydrophilic acids isolated at the alpine site had a lower C:N ratio than those isolated at the forested site. Similarly, the C:N ratio of organic acids at both sites was lower in September than in June during peak runoff. These differences appear to be a result of changes in both DOM precursor material and hydrologic flowpaths. Using C:N ratios of fulvic and hydrophilic acids, we estimate that nonhumic material carried between 54 to 73% of the organic N in surface water at the alpine site and 44 to 58% of the organic N in surface water at the subalpine site.     

Identification and Characterization of Endothelin Receptor Subtype B in Rat Retina

Abstract: The presence of immunoreactive (IR) endothelin (ET)-1 and ET-1 receptors in rat retina has been studied by radioimmunoassay and receptor assay, respectively. The specific binding of ¹²⁵I-ET-1 to rat retinal particulate preparations was saturable. Apparent equilibrium conditions were established within 120–140 min. Scatchard analysis of binding data indicated a single class of high-affinity binding sites with a K _D of 35 ± 11 p M and a B_max of 168 ± 60 fmol/mg of protein. ¹²⁵I-ET-1 binding to retinal particulate preparations was not inhibited by 1 μ M concentrations of somatostatin, atrial natriuretic factor, brain natriuretic peptide, thyroid-stimulating hormone, growth hormone, or insulin. The three endothelin isoforms, ET-1,-2, and-3, had similar affinity for the receptor. Cross-linking of ¹²⁵I-ET-1 to retinal particulate preparations with disuccinimidyl suberate resulted in the labeling of two bands with apparent molecular masses of 52 and 34 kDa. We have established a highly sensitive and specific radioimmunoassay for ET-1. The concentration of IR-ET-1 in rat retina was 35 ± 10 fmol/g wet weight. The demonstration of specific high-affinity ETB receptors and the presence of IR-ET-1 suggest that the peptide may act as a neurotransmitter or neuro-modulator in the retina.     

Groundwater controls on nutrient cycling in a Mojave desert stream

1. Groundwater fluxes of nitrogen and dissolved organic carbon (DOC) were investigated in Grape Vine Canyon Stream in the Mojave Desert focusing on the rate of inputs and the fate of groundwater-derived nutrients in the stream. Discharge rates from different ground waters were measured using an end-member mixing model coupled with injections of a conservative solute tracer into the stream channel.
2. In surface water, nitrate concentration averaged 1.13 mg N L^–1 and DOC concentration averaged 1.82 mg C L^–1.
3. Groundwater discharge into Grape Vine Canyon Stream was derived from three sources. Nitrate concentration varied among the three groundwater sources with mean concentrations of 0.56, 0.94 and 0.08 mg N L^–1. DOC, in contrast, did not vary among ground water sources, with an overall average concentration of 2.96 mg C L^–1.
4. In the surface stream, nitrate concentration was two-fold greater than the concentration predicted from groundwater input, indicating that in-stream processes generated nitrate. Stream DOC concentration was lower than predicted based upon groundwater input rate. The production of nitrate and loss of DOC suggest that DOC is lost through mineralisation of dissolved organic matter, possibly resulting in the mineralisation of dissolved organic nitrogen to ammonium and subsequent transformation to nitrate via nitrification. In further support of this hypothesised linkage, DOC loss explained 80–89% of the variance in nitrate production in Grape Vine Canyon Stream.     

Does ionic strength affect the configuration of aquatic humic substances,as indicated by gel filtration?

SUMMARY. 1. The effect of ionic strength on the configuration of aquatic humic substances was studied by gel filtration and dialysis of water from small. Finnish forest lakes of varying colour.
2. Sephadex gel filtration of water from the most humic lake gave similar elution profiles of UV absorbance and dissolved organic carbon (DOC). Gel filtration of unconcentrated samples from all three lakes under natural conditions of ionic strength (I = 1.7 × 10⁻⁴) and pH (5.5–6.0) gave similar fractionation of humic substances, despite their widely differing colour (30–350 mg Pt l⁻¹) and DOC (5–25mg C l⁻¹).
3. Increasing the ionic strength by two orders of magnitude caused considerable retardation on the Sephadex columns of the humic substances, suggesting a decrease in their molecular size and/or shape.
4. Dialysis experiments strongly indicated that ionic strength-induced changes in the configuration of the aquatic humic substances are indeed real. Hence it is probable that the elution behaviour of aquatic humic substances on Sephadex gels has previously been wrongly attributed to ionic strength-dependent interactions between the gel and the humic substances.     

Comparison of measured and modelled copper binding by natural organic matter in freshwaters

Fifteen freshwater samples containing significant concentrations of dissolved organic carbon-[DOC]-were titrated with copper under standardised conditions (pH 6 and 7), and concentrations of Cu(2+)-[Cu(2+)]-were measured with an ion-selective electrode. Measured values of [Cu(2+)], which were in the range 10(-11)-10(-5) moll(-1), were compared with those simulated using Humic Ion-Binding Models V and VI. It was assumed that copper speciation was controlled by the organic matter, represented by fulvic acid (FA), together with inorganic solution complexation (calculated with an inorganic speciation model). The models were calibrated by adjusting a single quantity, the concentration of FA. The optimised value-[FA](opt)-was that giving the best agreement, according to least squares, between measured and simulated [Cu(2+)]. The calculations took into account competition by other dissolved (filterable) metals (Mg, Al, Ca, Fe(II), Fe(III), Zn); in the case of Fe(III) it was assumed either that all the dissolved metal was truly in solution, or that the activity of Fe(3+) was controlled by equilibrium with Fe(OH)(3). The assumption about Fe(III) had relatively small effects on the fitting of Model V, but was significant for Model VI, because Model VI represents low-abundance, high-affinity binding sites in humic matter, which are sensitive to Fe(III) competition. Because of its inclusion of the high-affinity sites, Model VI provided better fits of the data than did Model V. Furthermore, Model VI with Fe(3+) activity controlled by Fe(OH)(3) gave smaller variation in the ratio of [FA](opt) to [DOC] than Model VI with all Fe(III) assumed to be in solution. The average [FA](opt)/[DOC] found from the Cu titrations was 1.30, which implies that 65% of the organic matter is 'active' with respect to metal binding. The average ratio of 1.30 is in reasonable agreement with ratios obtained by applying the model to field data sets for charge balance (1.22), Al speciation (1.56) and base titrations of Cu-amended waters (1.45). It is concluded that Model VI/Fe(OH)(3) provides the most reliable predictions of dissolved metal speciation in natural waters; at a total Cu concentration of 1 microM, the predicted concentration of Cu(2+) is expected to be correct to within a factor of 3.6 in 95% of cases.