... J. 123,41-55 Giorgi, E. P., Moses, T. F., Grant, JK, Scott, R. & Sinclair, J. (1974) Mol.... more ... J. 123,41-55 Giorgi, E. P., Moses, T. F., Grant, JK, Scott, R. & Sinclair, J. (1974) Mol. ... Chain Fatty Acids and Related Compounds with a Low-Molecular-Weight Carcinogen-Binding Protein from Rat Liver EDWARD TIPPING, BRIAN KETTERER, LUCIA CHRISTODOULIDES and ...
1. The interactions of ferriprotoporphyrin IX with ligandin and aminoazo-dye-binding protein A re... more 1. The interactions of ferriprotoporphyrin IX with ligandin and aminoazo-dye-binding protein A result in absorption spectra in the Soret region characteristic of the ligand in its monomeric state. 2. Both proteins are able to bind ferrous as well as ferric haem. 3. Ferriprotoporphyrin IX is bound at a single site on both proteins. At pH7.0, I 0.16M, difference-spectrophotometric measurements gave association constants of 10(7) and 4 X 10(6) LITRE/MOL FOR LIGANDIN AND PROTEin A respectively. Under the same conditions fluorescence-quenching experiments gave an association constant of 2 X 10(7) litre/mol for ligandin. 4. Bilirubin, bromosulphophthalein and oesterone sulphate each compete with haem for binding by the two proteins. 5. Ferriprotoporphyrin IX bound to both ligandin and protein A is able to form co-ordination complexes with CN-, but not, to any measurable extent, with either N3- or F-. From these results it is suggested that binding by the two proteins may not involve the h...
Ligandin and aminoazo-dye-binding protein A both bind bilirubin at a single site. Quantitative st... more Ligandin and aminoazo-dye-binding protein A both bind bilirubin at a single site. Quantitative studies of the interactions using difference spectrophotometry show that at pH 7.0, protein A binds the tetrapyrrole with an association constant (K) greater than or equal to 2 X 10(7) litre/mol, whereas binding by ligandin is slightly weaker (K = 7 X 10(6) litre/mol) at this pH. The protein-bilirubin complexes give rise to absorption and fluorescence spectra quite different from those of unbound bilirubin and also to large Cotton effects. It appears that on binding to both proteins, the ligand is forced into a rigid twisted configuration in a hydrophobic environment. Ligandin and protein A resemble serum albumin in their interactions with bilirubin.
A protein of S20,W 1.6S and mol.wt. 14000, which binds covalently a metabolite of the aminoazodye... more A protein of S20,W 1.6S and mol.wt. 14000, which binds covalently a metabolite of the aminoazodye carcinogen NN-dimethyl-4-amino-3'-methylazobenzene, was isolated from rat liver cytosol from both carcinogen-treated and normal rats. The protein binds non-covalently palmitoyl-CoA, fatty acids, bilirubin, sex steroids and their sulphates, bile acids and salts, bromosulphophthalein, diethylstilboestrol and 20-methylcholanthrene with a wide range of affinities. The protein is isolated as three components with isoelectric points of 5.0, 5.9 and 7.6 by a method involving isoelectric focusing. All three components have closely similar amino acid analyses, tryptic-peptide 'maps' and u.v. spectra. Each single component redistributes into all three on further electrophoresis. However, the three forms differ in their binding characteristics, the form of pI 7.6 having much the highest affinity for compounds bound non-covalently. The protein was identified immunologically in rat liver...
An exhausted sand quarry which had filled with acid water (pH 3) from the oxidation of pyrite was... more An exhausted sand quarry which had filled with acid water (pH 3) from the oxidation of pyrite was treated with calcium hydroxide to neutralize the water (pH 8), and sewage sludge to prevent further ingress of acid. The water remained neutral for 2 years, an appreciable quantity of base being generated by the reduction of sulphate to sulphide in the anoxic sediment formed by the sewage sludge. After this time the water reverted to acid conditions, chiefly because the lake was too shallow to retain the sewage sludge over a sufficiently large area of its bed. Incubation experiments showed that the sewage sludge had a large capacity for sulphate reduction, which was equally efficient in acid or neutral waters and that the areal rate of consumption was sufficiently fast to neutralize all incoming acid, if at least 50% of the lake bed was covered with sludge. Throughout the course of the field investigations there was no foul smell and the lake was quickly colonized by phytoplankton, macr...
... of biogeochemical processes, in cluding pH buffering, nutrient cycling, ionic balance, minera... more ... of biogeochemical processes, in cluding pH buffering, nutrient cycling, ionic balance, mineral weathering, metal leaching, and pollutant toxicity, mobility, and bioavailability (Hemond 1980; 537 538 MJ Scott et al. Cronan and Aiken 1985; Pohlman and McColl 1988; Vance and ...
Model UV absorbance a b s t r a c t We present a model that considers UV-absorbing dissolved orga... more Model UV absorbance a b s t r a c t We present a model that considers UV-absorbing dissolved organic matter (DOM) to consist of two components (A and B), each with a distinct and constant spectrum. Component A absorbs UV light strongly, and is therefore presumed to possess aromatic chromophores and hydrophobic character, whereas B absorbs weakly and can be assumed hydrophilic. We parameterised the model with dissolved organic carbon concentrations [DOC] and corresponding UV spectra for c. 1700 filtered surface water samples from North America and the United Kingdom, by optimising extinction coefficients for A and B, together with a small constant concentration of non-absorbing DOM (0.80 mg DOC L À1 ). Good unbiased predictions of [DOC] from absorbance data at 270 and 350 nm were obtained (r 2 ¼ 0.98), the sum of squared residuals in [DOC] being reduced by 66% compared to a regression model fitted to absorbance at 270 nm alone. The parameterised model can use measured optical absorbance values at any pair of suitable wavelengths to calculate both [DOC] and the relative amounts of A and B in a water sample, i.e. measures of quantity and quality. Blind prediction of [DOC]
... This work was supported by the European Economic Community, the Natural Environment Research ... more ... This work was supported by the European Economic Community, the Natural Environment Research ... REFERENCES Backes CA and Tipping E. (1986) Aluminium complex-ation by an aquatic ... An evaluation of the use of cation-exchange resin for the determination of organically ...
ABSTRACT Natural capital and ecosystem service concepts are embodied in the ecosystems approach t... more ABSTRACT Natural capital and ecosystem service concepts are embodied in the ecosystems approach to sustainable development, which is a framework being consistently adopted by decision making bodies ranging from national governments to the United Nations. In the Millennium Ecosystem Assessment soils are given the vital role of a supporting service, but many of the other soil goods and services remain obscured. In this review we address this using and earth-system approach, highlighting the final goods and services soils produce, in a stock-fund, fund-service model of the pedosphere. We also argue that focusing on final goods and services will be counterproductive in the long run and emphasize that final goods and services are derived from an ecosystem supply chain that relies on ecological infrastructure. We propose that an appropriate ecosystems framework for soils should incorporate soil stocks (natural capital) showing their contribution to stock-flows and emergent fund-services as part of the supply chain. By so doing, an operational ecosystems concept for soils can draw on much more supporting data on soil stocks as demonstrated in a case study with soils data from England and Wales showing stocks, gaps in monitoring and drivers of change. Although the focus of this review is on soils, we believe the earth-system approach and principles of the ecosystem supply chain are widely applicable to the ecosystems approach and bring clarity in terms of where goods and services are derived from.
The Windermere Humic Aqueous Model (WHAM) incorporating Humic Ion-Binding Model VI was applied to... more The Windermere Humic Aqueous Model (WHAM) incorporating Humic Ion-Binding Model VI was applied to analytical data from the United Kingdom Acid Waters Monitoring Network, collected for 22 streams and lakes over the period 1988-2007, to calculate the chemical speciation of monomeric aluminium (Al(mon)) in 3087 water samples. Model outputs were compared with analytical measurements of labile and non-labile Al(mon) concentrations, the former being equated with inorganic forms of Al(mon) and the latter with organically-complexed metal. Raw analytical data were used, and also data produced by applying a correction for the possible dissociation of organically-complexed Al(mon), and therefore its underestimation, during passage through the analytical cation-exchange column. Model calibration was performed by finding the conversion factor, F(FADOC), between the concentration of isolated fulvic acid, with default ion-binding properties, required by the model, and the measured concentration of dissolved organic carbon, [DOC]. For both uncorrected and corrected data, the value of F(FADOC) for streams was greater than for lakes, indicating greater binding activity towards aluminium. Model fits were better using uncorrected analytical data, but the values of F(FADOC) obtained from corrected data agreed more closely with previous estimates. The model provided reasonably good explanations of differences in aluminium speciation between sampling sites, and of temporal variations at individual sites. With total monomeric concentration as input, WHAM calculations might substitute for analytical speciation measurements, or aid analytical quality control. Calculated Al(3+) activities, a(Al3+), showed a pH-dependence similar to that previously found for other surface waters, and the modelling exercise identified differences between waters of up to two orders of magnitude in the value of a(Al3+) at a given pH. The model gives the net charge of dissolved organic matter, which is calculated to have risen significantly at 15 of the AWMN sites, due to increases in pH and decreases in aluminium concentration.
The functional properties of dissolved organic matter (DOM) from Rough Sike, a stream draining bl... more The functional properties of dissolved organic matter (DOM) from Rough Sike, a stream draining blanket peat in the northern Pennines, UK, were investigated using a series of 12 standardised assays. Nine stream samples were collected at different discharges during 2003--2006, and DOM concentrates obtained by low temperature rotary evaporation. Suwannee River Fulvic Acid was used as a quality control standard in the assays. Dissolved organic matter in high-discharge samples was more light-absorbing at 280 and 340 nm and adsorbed more strongly to alumina, than DOM characteristic of low streamflow, but was less fluorescent and hydrophilic, and poorer in proton-dissociating groups. No significant differences were found in light absorption at 254 nm, copper- or benzo(a)pyrene binding, or photochemical fading. Combination of the Rough Sike data with previously-published results for other streams and a lake yields totals of 20-23 values per assay, for a range of DOM types. For the combined data, variability in all the assays is significant (p < 0.001), as judged by comparison with variations in repeat measurements on the quality control standard. Analysis of the combined data shows that DOM hydrophilicity and adsorption are well-predicted by linear relationships with the extinction coefficient at 340 nm (E340), while good quadratic relationships exist between E340 and both buffering capacity and fluorescence.
Dissolved organic carbon (DOC) concentrations in soil water samples collected from depths of 5 to... more Dissolved organic carbon (DOC) concentrations in soil water samples collected from depths of 5 to 20 cm at 10 moorland and 11 forest sites during the period 2000-2006 were obtained from new measurements and from the monitoring programmes of the UK Environmental Change Network and the International Cooperative Programme (ICP) on Forests. Data on soil properties and vegetation type were also assembled. Considering data from Prenart tension collectors, which were used at nearly all the sites, mean annual concentrations ranged from 1.3 to 97.5 g m(-3) with means of 19.5 (standard deviation 15.2) and 27.6 (SD 23.3) g m(-3) for moorland and forest sites respectively. Interannual mean DOC concentration at an individual site varied by only 1.5-fold, averaged over all sites with at least three years' data. Concentrations during summer months (April to September) were on average 17% greater than those in winter (October to March). If data from two sites (the single peatland and an unusual forest site) were ignored, DOC concentrations were strongly inversely related to water flux, estimated from rainfall and evaporation data. Fluxes of DOC, calculated by combining concentration with water flux, ranged from 2.2 to 71.9 gC m(-2) yr(-1) over all sites and years, with overall means of 19.2 (SD 13.6) and 12.2 (SD 13.9) gC m(-2) yr(-1) for the moorland and forest sites respectively. However, if the two exceptional sites were omitted, the overall mean was 9.1 gC m(-)(2) yr(-1) with a standard deviation of only 4.9 gC m(-2) yr(-1). Annual DOC flux was strongly dependent upon annual water flux, varying by 3.5-fold between years when averaged over all sites. On average, 75.5% of the DOC was exported during the winter period (October to March).
... J. 123,41-55 Giorgi, E. P., Moses, T. F., Grant, JK, Scott, R. & Sinclair, J. (1974) Mol.... more ... J. 123,41-55 Giorgi, E. P., Moses, T. F., Grant, JK, Scott, R. & Sinclair, J. (1974) Mol. ... Chain Fatty Acids and Related Compounds with a Low-Molecular-Weight Carcinogen-Binding Protein from Rat Liver EDWARD TIPPING, BRIAN KETTERER, LUCIA CHRISTODOULIDES and ...
1. The interactions of ferriprotoporphyrin IX with ligandin and aminoazo-dye-binding protein A re... more 1. The interactions of ferriprotoporphyrin IX with ligandin and aminoazo-dye-binding protein A result in absorption spectra in the Soret region characteristic of the ligand in its monomeric state. 2. Both proteins are able to bind ferrous as well as ferric haem. 3. Ferriprotoporphyrin IX is bound at a single site on both proteins. At pH7.0, I 0.16M, difference-spectrophotometric measurements gave association constants of 10(7) and 4 X 10(6) LITRE/MOL FOR LIGANDIN AND PROTEin A respectively. Under the same conditions fluorescence-quenching experiments gave an association constant of 2 X 10(7) litre/mol for ligandin. 4. Bilirubin, bromosulphophthalein and oesterone sulphate each compete with haem for binding by the two proteins. 5. Ferriprotoporphyrin IX bound to both ligandin and protein A is able to form co-ordination complexes with CN-, but not, to any measurable extent, with either N3- or F-. From these results it is suggested that binding by the two proteins may not involve the h...
Ligandin and aminoazo-dye-binding protein A both bind bilirubin at a single site. Quantitative st... more Ligandin and aminoazo-dye-binding protein A both bind bilirubin at a single site. Quantitative studies of the interactions using difference spectrophotometry show that at pH 7.0, protein A binds the tetrapyrrole with an association constant (K) greater than or equal to 2 X 10(7) litre/mol, whereas binding by ligandin is slightly weaker (K = 7 X 10(6) litre/mol) at this pH. The protein-bilirubin complexes give rise to absorption and fluorescence spectra quite different from those of unbound bilirubin and also to large Cotton effects. It appears that on binding to both proteins, the ligand is forced into a rigid twisted configuration in a hydrophobic environment. Ligandin and protein A resemble serum albumin in their interactions with bilirubin.
A protein of S20,W 1.6S and mol.wt. 14000, which binds covalently a metabolite of the aminoazodye... more A protein of S20,W 1.6S and mol.wt. 14000, which binds covalently a metabolite of the aminoazodye carcinogen NN-dimethyl-4-amino-3'-methylazobenzene, was isolated from rat liver cytosol from both carcinogen-treated and normal rats. The protein binds non-covalently palmitoyl-CoA, fatty acids, bilirubin, sex steroids and their sulphates, bile acids and salts, bromosulphophthalein, diethylstilboestrol and 20-methylcholanthrene with a wide range of affinities. The protein is isolated as three components with isoelectric points of 5.0, 5.9 and 7.6 by a method involving isoelectric focusing. All three components have closely similar amino acid analyses, tryptic-peptide 'maps' and u.v. spectra. Each single component redistributes into all three on further electrophoresis. However, the three forms differ in their binding characteristics, the form of pI 7.6 having much the highest affinity for compounds bound non-covalently. The protein was identified immunologically in rat liver...
An exhausted sand quarry which had filled with acid water (pH 3) from the oxidation of pyrite was... more An exhausted sand quarry which had filled with acid water (pH 3) from the oxidation of pyrite was treated with calcium hydroxide to neutralize the water (pH 8), and sewage sludge to prevent further ingress of acid. The water remained neutral for 2 years, an appreciable quantity of base being generated by the reduction of sulphate to sulphide in the anoxic sediment formed by the sewage sludge. After this time the water reverted to acid conditions, chiefly because the lake was too shallow to retain the sewage sludge over a sufficiently large area of its bed. Incubation experiments showed that the sewage sludge had a large capacity for sulphate reduction, which was equally efficient in acid or neutral waters and that the areal rate of consumption was sufficiently fast to neutralize all incoming acid, if at least 50% of the lake bed was covered with sludge. Throughout the course of the field investigations there was no foul smell and the lake was quickly colonized by phytoplankton, macr...
... of biogeochemical processes, in cluding pH buffering, nutrient cycling, ionic balance, minera... more ... of biogeochemical processes, in cluding pH buffering, nutrient cycling, ionic balance, mineral weathering, metal leaching, and pollutant toxicity, mobility, and bioavailability (Hemond 1980; 537 538 MJ Scott et al. Cronan and Aiken 1985; Pohlman and McColl 1988; Vance and ...
Model UV absorbance a b s t r a c t We present a model that considers UV-absorbing dissolved orga... more Model UV absorbance a b s t r a c t We present a model that considers UV-absorbing dissolved organic matter (DOM) to consist of two components (A and B), each with a distinct and constant spectrum. Component A absorbs UV light strongly, and is therefore presumed to possess aromatic chromophores and hydrophobic character, whereas B absorbs weakly and can be assumed hydrophilic. We parameterised the model with dissolved organic carbon concentrations [DOC] and corresponding UV spectra for c. 1700 filtered surface water samples from North America and the United Kingdom, by optimising extinction coefficients for A and B, together with a small constant concentration of non-absorbing DOM (0.80 mg DOC L À1 ). Good unbiased predictions of [DOC] from absorbance data at 270 and 350 nm were obtained (r 2 ¼ 0.98), the sum of squared residuals in [DOC] being reduced by 66% compared to a regression model fitted to absorbance at 270 nm alone. The parameterised model can use measured optical absorbance values at any pair of suitable wavelengths to calculate both [DOC] and the relative amounts of A and B in a water sample, i.e. measures of quantity and quality. Blind prediction of [DOC]
... This work was supported by the European Economic Community, the Natural Environment Research ... more ... This work was supported by the European Economic Community, the Natural Environment Research ... REFERENCES Backes CA and Tipping E. (1986) Aluminium complex-ation by an aquatic ... An evaluation of the use of cation-exchange resin for the determination of organically ...
ABSTRACT Natural capital and ecosystem service concepts are embodied in the ecosystems approach t... more ABSTRACT Natural capital and ecosystem service concepts are embodied in the ecosystems approach to sustainable development, which is a framework being consistently adopted by decision making bodies ranging from national governments to the United Nations. In the Millennium Ecosystem Assessment soils are given the vital role of a supporting service, but many of the other soil goods and services remain obscured. In this review we address this using and earth-system approach, highlighting the final goods and services soils produce, in a stock-fund, fund-service model of the pedosphere. We also argue that focusing on final goods and services will be counterproductive in the long run and emphasize that final goods and services are derived from an ecosystem supply chain that relies on ecological infrastructure. We propose that an appropriate ecosystems framework for soils should incorporate soil stocks (natural capital) showing their contribution to stock-flows and emergent fund-services as part of the supply chain. By so doing, an operational ecosystems concept for soils can draw on much more supporting data on soil stocks as demonstrated in a case study with soils data from England and Wales showing stocks, gaps in monitoring and drivers of change. Although the focus of this review is on soils, we believe the earth-system approach and principles of the ecosystem supply chain are widely applicable to the ecosystems approach and bring clarity in terms of where goods and services are derived from.
The Windermere Humic Aqueous Model (WHAM) incorporating Humic Ion-Binding Model VI was applied to... more The Windermere Humic Aqueous Model (WHAM) incorporating Humic Ion-Binding Model VI was applied to analytical data from the United Kingdom Acid Waters Monitoring Network, collected for 22 streams and lakes over the period 1988-2007, to calculate the chemical speciation of monomeric aluminium (Al(mon)) in 3087 water samples. Model outputs were compared with analytical measurements of labile and non-labile Al(mon) concentrations, the former being equated with inorganic forms of Al(mon) and the latter with organically-complexed metal. Raw analytical data were used, and also data produced by applying a correction for the possible dissociation of organically-complexed Al(mon), and therefore its underestimation, during passage through the analytical cation-exchange column. Model calibration was performed by finding the conversion factor, F(FADOC), between the concentration of isolated fulvic acid, with default ion-binding properties, required by the model, and the measured concentration of dissolved organic carbon, [DOC]. For both uncorrected and corrected data, the value of F(FADOC) for streams was greater than for lakes, indicating greater binding activity towards aluminium. Model fits were better using uncorrected analytical data, but the values of F(FADOC) obtained from corrected data agreed more closely with previous estimates. The model provided reasonably good explanations of differences in aluminium speciation between sampling sites, and of temporal variations at individual sites. With total monomeric concentration as input, WHAM calculations might substitute for analytical speciation measurements, or aid analytical quality control. Calculated Al(3+) activities, a(Al3+), showed a pH-dependence similar to that previously found for other surface waters, and the modelling exercise identified differences between waters of up to two orders of magnitude in the value of a(Al3+) at a given pH. The model gives the net charge of dissolved organic matter, which is calculated to have risen significantly at 15 of the AWMN sites, due to increases in pH and decreases in aluminium concentration.
The functional properties of dissolved organic matter (DOM) from Rough Sike, a stream draining bl... more The functional properties of dissolved organic matter (DOM) from Rough Sike, a stream draining blanket peat in the northern Pennines, UK, were investigated using a series of 12 standardised assays. Nine stream samples were collected at different discharges during 2003--2006, and DOM concentrates obtained by low temperature rotary evaporation. Suwannee River Fulvic Acid was used as a quality control standard in the assays. Dissolved organic matter in high-discharge samples was more light-absorbing at 280 and 340 nm and adsorbed more strongly to alumina, than DOM characteristic of low streamflow, but was less fluorescent and hydrophilic, and poorer in proton-dissociating groups. No significant differences were found in light absorption at 254 nm, copper- or benzo(a)pyrene binding, or photochemical fading. Combination of the Rough Sike data with previously-published results for other streams and a lake yields totals of 20-23 values per assay, for a range of DOM types. For the combined data, variability in all the assays is significant (p < 0.001), as judged by comparison with variations in repeat measurements on the quality control standard. Analysis of the combined data shows that DOM hydrophilicity and adsorption are well-predicted by linear relationships with the extinction coefficient at 340 nm (E340), while good quadratic relationships exist between E340 and both buffering capacity and fluorescence.
Dissolved organic carbon (DOC) concentrations in soil water samples collected from depths of 5 to... more Dissolved organic carbon (DOC) concentrations in soil water samples collected from depths of 5 to 20 cm at 10 moorland and 11 forest sites during the period 2000-2006 were obtained from new measurements and from the monitoring programmes of the UK Environmental Change Network and the International Cooperative Programme (ICP) on Forests. Data on soil properties and vegetation type were also assembled. Considering data from Prenart tension collectors, which were used at nearly all the sites, mean annual concentrations ranged from 1.3 to 97.5 g m(-3) with means of 19.5 (standard deviation 15.2) and 27.6 (SD 23.3) g m(-3) for moorland and forest sites respectively. Interannual mean DOC concentration at an individual site varied by only 1.5-fold, averaged over all sites with at least three years' data. Concentrations during summer months (April to September) were on average 17% greater than those in winter (October to March). If data from two sites (the single peatland and an unusual forest site) were ignored, DOC concentrations were strongly inversely related to water flux, estimated from rainfall and evaporation data. Fluxes of DOC, calculated by combining concentration with water flux, ranged from 2.2 to 71.9 gC m(-2) yr(-1) over all sites and years, with overall means of 19.2 (SD 13.6) and 12.2 (SD 13.9) gC m(-2) yr(-1) for the moorland and forest sites respectively. However, if the two exceptional sites were omitted, the overall mean was 9.1 gC m(-)(2) yr(-1) with a standard deviation of only 4.9 gC m(-2) yr(-1). Annual DOC flux was strongly dependent upon annual water flux, varying by 3.5-fold between years when averaged over all sites. On average, 75.5% of the DOC was exported during the winter period (October to March).
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