Granulation of activated sludge in a pilot-scale sequencing batch reactor for the treatment of low-strength municipal wastewater

Aerobic granulation of activated sludge was achieved in a pilot-scale sequencing batch reactor (SBR) for the treatment of low-strength municipal wastewater (<200 mg L⁻¹ of COD, chemical oxygen demand). The volume exchange ratio and settling time of an SBR were found to be two key factors in the granulation of activated sludge grown on the low-strength municipal wastewater. After operation of 300 days, the mixed liquor suspended solids (MLSS) concentration in the SBR reached 9.5 g L⁻¹ and consisted of approximate 85% granular sludge. The average total COD removal efficiency kept at 90% and NH₄⁺-N was almost completely depleted (∼95%) after the formation of aerobic granules. The granules (with a diameter over 0.212 mm) had a diameter ranging from 0.2 to 0.8 mm and had good settling ability with a settling velocity of 18-40 m h⁻¹. Three bacterial morphologies of rod, coccus and filament coexisted in the granules. Mathematical modeling was performed to get insight into this pilot-scale granule-based reactor. The modified IWA activated sludge model No 3 (ASM3) was able to adequately describe the pilot-scale SBR dynamics during its cyclic operation.     

Evaluation of the particle measurement programme (PMP) protocol to remove the vehicles' exhaust aerosol volatile phase

European regulation for Euro 5/6 light duty emissions introduced the measurement of non-volatile particles with diameter > 23 nm. The volatile phase is removed by using a heated dilution stage (150 °C) and a heated tube (at 300-400 °C). We investigated experimentally the removal efficiency for volatile species of the specific protocol by conducting measurements with two Euro 3 diesel light duty vehicles, a Euro 2 moped, and a Euro III heavy duty vehicle with the system's heaters on and off. The particle number distributions were measured with a Scanning Mobility Particle Sizer (SMPS) and a Fast Mobility Particle Sizer (FMPS). An Aerosol Mass Spectrometer (AMS) was used to identify the non-refractory chemical composition of the particles. A Multi-Angle Absorption Photometer (MAAP) was used to measure the black carbon concentration. The results showed that the condensed material in the accumulation mode (defined here as particles in the diameter range of ∼ 50-500 nm) was removed with an efficiency of 50-90%. The (volatile) nucleation mode was also completely evaporated or was decreased to sizes < 23 nm; thus these particles wouldn't be counted from the particle counter, indicating the robustness of the protocol.     

Thiol-functionalised mesoporous silica-coated magnetite nanoparticles for high efficiency removal and recovery of Hg from water

The preparation and testing of thiol-functionalised silica-coated magnetite nanoparticles (TF-SCMNPs) is described. The characteristics of these particles are assessed at different stages in the production process using X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), and a magnetometer. The particles were found to be almost spherical with a uniform mesoporous structure with a pore size of ∼2.1 nm. The particles were strongly responsive to an external magnetic field making separation from solution possible in less than 1 min. The adsorption characteristics of the particles were quantified in a series of isotherm experiments using Hg(II) solution concentrations between 40 and 1000 μg l⁻¹ at adsorbent concentrations of 4 and 8 mg l⁻¹. The adsorption capacity was higher than for other commonly used adsorbents with 90% of Hg(II) removed during the first 5 min and equilibrium in less than 15 min. Both the Langmuir and Freundlich isotherm models were applied to the isotherm data and the maximum adsorption capacity was achieved when the ratio of adsorbent to adsorbate was low. Both temperature and pH had an effect on adsorption but when the TF-SCMNPs were used for removal of Hg(II) from tap water and bottled water, which contained other ions, there appeared to be no interference. Hg(II) could be successfully desorbed using thiourea in a 3 M HCl solution; this did not result in the destruction of the nanoparticles and they could subsequently be reused without loss of their activity in repetitive adsorption tests.     

Nitrogen and phosphorus removal from an abattoir wastewater in a SBR with aerobic granular sludge

The formation and performance of granular sludge was studied in an 8 l sequencing batch reactor (SBR) treating an abattoir (slaughterhouse) wastewater. Influent concentrations averaged 1520 mg l⁻¹ volatile suspended solids (VSS), 7685 mg l⁻¹ Chemical oxygen demand (COD), 1057 mg l⁻¹ total kjeldahl nitrogen (TKN), 217 mg l⁻¹ total P. The COD loading was 2.6 kg m⁻³ d⁻¹. The SBR was seeded with flocculating sludge from a SBR with an 1 h settle time, but granules developed within 4 days by reducing the settle time to 2 min. The SBR cycle also had 120 min mixed (anaerobic) fill, 220 min aerated react, and 18 min draw/idle. The granules had a mean diameter of 1.7 mm, a specific gravity of 1.035, a density of 62 g VSS l⁻¹, a zone settling velocity (ZSV) of 51 m h⁻¹, and a sludge volume index (SVI) of 22 ml g⁻¹. Without optimizing process conditions, removal of COD and P were over 98%, and removal of N and VSS were over 97%. Nitrification and denitrification occurred simultaneously during react. The results indicate that conventional SBRs treating wastewaters with flocculating sludge can be converted to granular SBRs by reducing the settle time.     

The effect of particle size on cardiovascular disorders--the smaller the worse

Background

Previous studies observed associations between airborne particles and cardio-vascular disease. Questions, however, remain as to which size of the inhalable particles (coarse, fine, or ultrafine) exerts the most significant impact on health.

Methods

For this retrospective study, data of the total number of 23,741 emergency service calls, registered between February 2002 and January 2003 in the City of Leipzig, were analysed, identifying 5326 as being related to cardiovascular incidences. Simultaneous particle exposure was determined for the particle sizes classes < 100 nm (UFP), < 2.5 μm (PM2.5) and < 10 μm (PM10). We used a time resolution of 1 day for both parameters, emergency calls and exposure.

Results

Within the group of cardiovascular diseases, the diagnostic category of hypertensive crisis showed a significant association with particle exposure. The significant effect on hypertensive crisis was found for particles with a size of < 100 nm in diameter and starting with a lag of 2 days after exposure. No consistent influence could be observed for PM2.5 and PM10. The Odds Ratios on hypertensive crisis were significant for the particle size < 100 nm in diameter from day 2 post exposure OR = 1.06 (95%CI: 1.02-1.10, p = 0.002) up to day 7 OR = 1.05 (95%CI 1.02-1.09, p = 0.005).

Conclusion

Ultrafine particles affect cardiovascular disease adversely, particularly hypertensive crises. Their effect is significant compared with PM2.5 and PM10. It appears necessary, from a public health point of view, to consider regulating this type of particles using appropriate measurands as particle number.     

Synthesis of monodispersed CMC-stabilized Fe-Cu bimetal nanoparticles for in situ reductive dechlorination of 1,2,4-trichlorobenzene

Monodispersed carboxymethyl cellulose (CMC)-stabilized Fe-Cu bimetal nanoparticles with an average diameter of less than 20 nm were successfully synthesized by a modified water-based approach. The as-resulting particles exhibit a core-shell structure and are quite uniform in size and shape. Batch experiments demonstrated that these nanoparticles could effectively dechlorinate 1,2,4-trichlorobenzene (1,2,4-TCB). Near 90% of reduction efficiency was achieved by CMC-stabilized Fe-Cu for 24 h treatment. By monitoring the reaction products with time by GC-MS, it was found that 1,2,4-TCB transformation mainly followed the sequential hydrogenolysis to 1,2-dichlorobenzene (12DCB), then chlorobenzene (CB) and eventually benzene. The pseudo first order 1,2,4-TCB degradation rate were 0.09 h⁻¹ and 0.06 h⁻¹ as CMC-to-Fe molar ratios were 0.00248 and 0.00124, respectively. Dechlorination mechanism was also proposed in this study.     

Assessment of human adenovirus removal in a full-scale membrane bioreactor treating municipal wastewater

Human adenoviruses (HAdVs) in wastewater samples taken from four different treatment stages of a full-scale municipal wastewater treatment plant (i.e., incoming raw sewage, primary sedimentation effluent, membrane bioreactor (MBR) influent, and MBR effluent) were quantified by real-time PCR assays to further estimate removal efficiency of the HAdVs. Based on hexon gene sequence comparisons, HAdV species A, C, and F were consistently found in the wastewater samples. In general, all three identified HAdV species were detected in most of the wastewater samples using the real-time PCR assays. Overall HAdV concentrations were rather stable over the entire 8-month study period (January-August, 2008) (approximately 10⁶-10⁷ viral particles/L of wastewater for the raw sewage and primary effluent; 10⁸-10⁹ viral particles/L for the MBR influent; and, 10³-10⁴ viral particles/L for the MBR effluent). No significant seasonal differences were noticed for the HAdV abundances. Removal efficiencies of the viral particles in the full-scale MBR process were assessed and showed an average HAdV removal of 5.0 ± 0.6 logs over the study period. The removal efficiencies for F species (average log removal of 6.5 ± 1.3 logs) were typically higher (p-value <0.05) than those of the other two species (average of 4.1 ± 0.9 and 4.6 ± 0.5 logs for species A and C, respectively). These results demonstrate that the full-scale MBR system efficiently removed most HAdV from the wastewater leaving about 10³ viral particles/L in the MBR effluent.     

Low-cost struvite production using source-separated urine in Nepal

This research investigated the possibility of transferring phosphorus from human urine into a concentrated form that can be used as fertilizer in agriculture. The community of Siddhipur in Nepal was chosen as a research site, because there is a strong presence and acceptance of the urine-diverting dry toilets needed to collect urine separately at the source. Furthermore, because the mainly agricultural country is landlocked and depends on expensive, imported fertilizers, the need for nutrient security is high. We found that struvite (MgNH₄PO₄·6H₂O) precipitation from urine is an efficient and simple approach to produce a granulated phosphorus fertilizer. Bittern, a waste stream from salt production, is a practical magnesium source for struvite production, but it has to be imported from India. Calculations show that magnesium oxide produced from locally available magnesite would be a cheaper magnesium source. A reactor with an external filtration system was capable of removing over 90% of phosphorus with a low magnesium dosage (1.1 mol Mg mol P), with coarse nylon filters (pore width up to 160 ± 50 μm) and with only one hour total treatment time. A second reactor setup based on sedimentation only achieved 50% phosphate removal, even when flocculants were added. Given the current fertilizer prices, high volumes of urine must be processed, if struvite recovery should be financially sustainable. Therefore, it is important to optimize the process. Our calculations showed that collecting the struvite and calcium phosphate precipitated spontaneously due to urea hydrolysis could increase the overall phosphate recovery by at least 40%. The magnesium dosage can be optimized by estimating the phosphate concentration by measuring electrical conductivity. An important source of additional revenue could be the effluent of the struvite reactor. Further research should be aimed at finding methods and technologies to recover the nutrients from the effluent.     

Concentrations of ultrafine particles at a highway toll collection booth and exposure implications for toll collectors

Research regarding the magnitude of ultrafine particle levels at highway toll stations is limited. This study measured ambient concentrations of ultrafine particles at a highway toll station from October 30 to November 1 and November 5 to November 6, 2008. A scanning mobility particle sizer was used to measure ultrafine particle concentrations at a ticket/cash tollbooth. Levels of hourly average ultrafine particles at the tollbooth were about 3-6 times higher than those in urban backgrounds, indicating that a considerable amount of ultrafine particles are exhausted from passing vehicles. A bi-modal size distribution pattern with a dominant mode at about < 6 nm and a minor mode at about 40 nm was observed at the tollbooth. The high amounts of nanoparticles in this study can be attributed to gas-to-particle reactions in fresh fumes emitted directly from vehicles. The influences of traffic volume, wind speed, and relative humidity on ultrafine particle concentrations were also determined. High ambient concentrations of ultrafine particles existed under low wind speed, low relative humidity, and high traffic volume. Although different factors account for high ambient concentrations of ultrafine particles at the tollbooth, measurements indicate that toll collectors who work close to traffic emission sources have a high exposure risk.     

Electrocatalytic characterization and dye degradation of Nano-TiO2 electrode films fabricated by CVD

A 20-40 nm anatase-titania film on a titanium electrode was fabricated using chemical vapor deposition (CVD). The film was characterized using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and atomic force microscopy (AFM). The CVD deposition time and number of deposition coatings were evaluated to establish the appropriate film fabrication parameters. Results indicate that two coatings at a deposition time of 6 h each produced the best nano-TiO₂ electrode films (NTEFs) with an even distribution of ca. 20 nm diameter nanoparticles in the anatase lattice. The NTEF was tested as an electrocatalytic anode to investigate the degradation efficiency in treating methyl orange dye wastewater. A high removal efficiency of methyl orange dye and total organic carbon (TOC) of 97 and 56%, respectively; was achieved using a current density of 20 mA cm^− 2 for 160 min. Cyclic voltammetry showed that the electrochemical degradation reaction rate at the NTEF surface was predominately driven by molecular diffusion. The electrocatalytic decomposition rate of organic pollutants at the NTEF is controlled by mass transport, which was associated with the nanostructure of the electrocatalytic electrode.     

Dynamic and distribution of ammonia-oxidizing bacteria communities during sludge granulation in an anaerobic-aerobic sequencing batch reactor

The structure dynamic of ammonia-oxidizing bacteria (AOB) community and the distribution of AOB and nitrite-oxidizing bacteria (NOB) in granular sludge from an anaerobic-aerobic sequencing batch reactor (SBR) were investigated. A combination of process studies, molecular biotechniques and microscale techniques were employed to identify and characterize these organisms. The AOB community structure in granules was substantially different from that of the initial pattern of the inoculants sludge. Along with granules formation, the AOB diversity declined due to the selection pressure imposed by process conditions. Denaturing gradient gel electrophoresis (DGGE) and sequencing results demonstrated that most of Nitrosomonas in the inoculating sludge were remained because of their ability to rapidly adapt to the settling-washing out action. Furthermore, DGGE analysis revealed that larger granules benefit more AOB species surviving in the reactor. In the SBR were various size granules coexisted, granule diameter affected the distribution range of AOB and NOB. Small and medium granules (d < 0.6 mm) cannot restrict oxygen mass transfer in all spaces of the sludge. Larger granules (d > 0.9 mm) can result in smaller aerobic volume fraction and inhibition of NOB growth. All these observations provide support to future studies on the mechanisms responsible for the AOB in granules systems.     

Emission characteristics of a heavy-duty diesel engine at simulated high altitudes

In order to evaluate the effects of altitude on the pollutant emissions of a diesel engine, an experimental research was carried out using an engine test bench with an altitude simulation system. The emissions of HC, CO, NOx, smoke, and particle number of a heavy-duty diesel engine were measured under steady state operating conditions at sea level and simulated altitudes of 1000 and 2000 m. The experimental results indicate that the high altitude increases the emissions of HC, CO and smoke of the diesel engine, the average increasing rates of which are 30%, 35% and 34% with addition of altitude of 1000 m, respectively. The effect of high altitudes on the NOx emission varies with the engine types and working conditions. At 1000 m the particles number emissions are 1.6 to 4.2 times the levels at the low altitude. The pattern of the particle size distributions at 1000 m is similar with that at sea-level, which is the mono-modal lognormal distribution with geometric mean diameter around 0.1 μm. However, the peak number concentrations of particles are bigger and the exhausted particles are smaller at the high altitude.     

Characterization of particle emission from household electrical appliances

The release of ultra-fine particles from equipment of daily use is currently a topic of high public concern. The present study reports on the measurement of 12 household appliances such as toasters, grills, and hair dryers in an emission test chamber regarding the release of particles between 5.6 and 560 nm. The devices were new at the time experiments started and had never been used for their original purpose. For instance, toasters and sandwich-makers were tested without the presence of food or residues from prior usage. During the experiments the devices released aerosols with count mean diameters mainly below 100 nm. Within the operating phase high quantities of 10 nm particles are released which form larger particles by agglomeration. The origin of the particles can be attributed to the heated surfaces but cleaning these surfaces only had a minor influence on the emission strength. The released particles are evaporated in a thermodenuder between 150 °C and 200 °C. These findings indicate the particles to be formed from semi-volatile organic compounds. However, the compounds are not located on the heated surfaces and are not released as supersaturated vapor because emission is continuous over the operating phase of the device. Furthermore, the contribution of oxygen to the formation process can be neglected because the emission can also be detected in a nitrogen atmosphere. However, the presence of additional organic compounds in the surrounding air was found to be influencing the growth of the particles within the operating phase. All in all the tested household appliances were strong particle emission sources even when there was no contact with food or clothing.     

The impact of alum based advanced nutrient removal processes on phosphorus bioavailability

Because eutrophication is a widespread consequence of wastewater discharges, there is a strong impetus to develop new approaches to remove phosphorus (P) from wastewater treatment plant (WWTP) effluents. We examined the effluents from a pilot plant that is testing various alum based processes for achieving > 99% P removal, however, it is not known how these advanced P removal technologies affect the bioavailability of P (BAP). We tested how the percent BAP (%BAP) varied with different P removal levels using an algal growth bioassay methodology. This facility reduced total P concentrations from ≈ 500 μg L⁻¹ in the pilot plant influent to 19 ± 4 (±SD) μg L⁻¹ in the final effluent, and our results showed that as the level of P removal increased, the %BAP of the product declined sharply, r² = 0.98. Prior to alum treatment, the influent had an average %BAP of 79 ± 13%, and after three steps of alum-based removal the %BAP averaged 7 ± 4%. Thus, this alum based P removal process was very effective at sequestering the P forms that most readily stimulate algal growth. Further, our results show the final BAP of the effluent was only ≈ 50% of the “reactive” P concentration. These results have important implications for nutrient management and trading schemes.     

Adsorption, sedimentation, and inactivation of E. coli within wastewater treatment wetlands

Bacteria fate and transport within constructed wetlands must be understood if engineered wetlands are to become a reliable form of wastewater treatment. This study investigated the relative importance of microbial treatment mechanisms in constructed wetlands treating both domestic and agricultural wastewater. Escherichia coli (E. coli) inactivation, adsorption, and settling rates were measured in the lab within two types of wastewater (dairy wastewater lagoon effluent and domestic septic tank effluent). In situ E. coli inactivation was also measured within a domestic wastewater treatment wetland and the adsorption of E. coli was also measured within the wetland effluent.Inactivation of E. coli appears to be the most significant contributor to E. coli removal within the wastewaters and wetland environments examined in this study. E. coli survived longer within the dairy wastewater (DW) compared to the domestic wastewater treatment wetland water (WW). First order rate constants for E. coli inactivation within the WW in the lab ranged from 0.09 day⁻¹ (d⁻¹) at 7.6 °C to 0.18 d⁻¹ at 22.8 °C. The average in situ rate constant observed within the domestic wetland ranged from 0.02 d⁻¹ to 0.03 d⁻¹ at an average water temperature of 17 °C. First order rate constants for E. coli inactivation within the DW ranged from 0.01 d⁻¹ at 7.7 °C to 0.04 d⁻¹ at 24.6 °C. Calculated distribution coefficients (K_d) were 19,000 mL g⁻¹, 324,000 mL g⁻¹, and 293 mL g⁻¹ for E. coli with domestic septic tank effluent (STE), treated wetland effluent (WLE), and DW, respectively. Approximately 50%, 20%, and 90% of E. coli were “free floating” or associated with particles <5 μm in size within the STE, WLE, and DW respectively. Although 10-50% of E. coli were found to associate with particles >5 μm within both the STE and DW, settling did not appear to contribute to E. coli removal within sedimentation experiments, indicating that the particles the bacteria were associated with had very small settling velocities.The results of this study highlight the importance of wastewater characterization when designing a treatment wetland system for bacterial removal. This study illustrated the level of variability in E. coli removal processes that can be observed within different wastewater, and wetland environments.     

Microorganisms and particles in AHU systems: Measurement and analysis

In this study, for better understanding the practical removal effect of air handling unit (AHU) system on airborne microorganisms (including bacteria and fungus) and particles and microbial growth, the samples of microorganisms and particles in 10 air handling unit (AHU) systems including fan coils and indoor air were collected and analyzed in air and component surfaces of such systems in two large public buildings. It is found that the removal efficiency is of the highest for bacteria 73.9% and the lowest for particles (0.5–2 μm) 24.4%. The surface concentration of equipment bacteria is 29 CFU/cm² and fungi 137 CFU/cm². Five of 10 systems have higher fungi concentrations on air intake than that on diffuser. The results also show that the central air supply system with common components (e.g., pre-filter and bag filter) has difficulty to achieve/maintain good performance once microorganisms and particles exist, especially for particle size D ≤ 3.3 μm. The size distribution has large influence on removal efficiency. The microbial growth on surfaces of duct and equipment was noticed and may be transferred into indoor air. This will decrease the indoor air quality and lead to adverse health effect.     

Effects of ultrasound on suspended particles in municipal wastewater

The objective of this research is to explore the fundamental characteristics of how particles in wastewater respond to ultrasound, with an aim to improve wastewater disinfection. Particles of a predetermined size fraction and concentration were treated with varying doses of ultrasound at 20.3 kHz. Ultrasonic power transfer to the fluid was measured using calorimetry or acoustical measurements. Image analysis particle counting was used to measure the size distribution of particles before and after ultrasound treatment. The influence of three parameters: particle origin (raw wastewater or from the aeration basin of the activated sludge process), particle concentration, and particle size on the percentage of particle breakage after ultrasound treatment was compared. It was found that raw wastewater and aeration basin particles of the same size fraction (90-106 μm) responded to ultrasound in a similar way. Particle breakage was not affected by changes in particle concentration from 100 to 400 particles per mL. Larger wastewater particles (90-250 μm) were more susceptible to breakage than smaller ones (38-63 μm diameter). The percentage of particle breakage increased linearly with a logarithmic increase in the ultrasound energy density, that is the ultrasound energy delivered per unit volume of the sample (R² = 0.48-0.91). An expression that predicts the percent of particles broken as a function of ultrasound energy density is provided.     

Removal of phosphorus from solution using biogenic iron oxides

Phosphorus removal by biogenic iron oxides was investigated, providing an initial characterization of a potentially regenerable iron-rich sorbent. The biogenic iron oxides were collected from a wetland ecosystem and were dominated by the sheaths of Leptothrix ochracea. Sorption kinetics followed a pseudo-1st order model (R² = 0.998) with a rate constant of 0.154 ± 0.013 h⁻¹. The Langmuir isotherm adequately described sorption for all samples (R² = 0.923-0.981); the Freundlich model was a better fit for only one of four samples. Maximum phosphorus sorption estimated using the Langmuir parameter ranged from 46.9 ± 2.9 to 165.0 ± 21.2 mg P/g Fe and was similar to other iron-rich substrates. Maximum sorption normalized to total solids ranged from 10.8 ± 0.7 to 39.9 ± 3.2 mg P/g, which represented the highest published values for iron-rich substrates. The high sorption capacity with respect to both iron and solids warrants further evaluation of biogenic iron oxides as a substrate for phosphorus removal.     

Remediation of metal-contaminated urban soil using flotation technique

A soil washing process using froth flotation technique was evaluated for the removal of arsenic, cadmium, copper, lead, and zinc from a highly contaminated urban soil (brownfield) after crushing of the particle-size fractions > 250 µm. The metal contaminants were in particulate forms and distributed in all the particle-size fractions. The particle-by-particle study with SEM-EDS showed that Zn was mainly present as sphalerite (ZnS), whereas Cu and Pb were mainly speciated as various oxide/carbonate compounds. The influence of surfactant collector type (non-ionic and anionic), collector dosage, pulp pH, a chemical activation step (sulfidization), particle size, and process time on metal removal efficiency and flotation selectivity was studied. Satisfactory results in metal recovery (42-52%), flotation selectivity (concentration factor > 2.5), and volume reduction (> 80%) were obtained with anionic collector (potassium amyl xanthate). The transportation mechanisms involved in the separation process (i.e., the true flotation and the mechanical entrainment) were evaluated by the pulp chemistry, the metal speciation, the metal distribution in the particle-size fractions, and the separation selectivity indices of Zn/Ca and Zn/Fe. The investigations showed that a great proportion of metal-containing particles were recovered in the froth layer by entrainment mechanism rather than by true flotation process. The non-selective entrainment mechanism of the fine particles (< 20 μm) caused a flotation selectivity drop, especially with a long flotation time (> 5 min) and when a high collector dose is used. The intermediate particle-size fraction (20-125 μm) showed the best flotation selectivity.     

Changes in water quality of the River Frome (UK) from 1965 to 2009: is phosphorus mitigation finally working?

The water quality of the River Frome, Dorset, southern England, was monitored at weekly intervals from 1965 until 2009. Determinands included phosphorus, nitrogen, silicon, potassium, calcium, sodium, magnesium, pH, alkalinity and temperature. Nitrate-N concentrations increased from an annual average of 2.4 mg l^− 1 in the mid to late 1960s to 6.0 mg l^− 1 in 2008-2009, but the rate of increase was beginning to slow. Annual soluble reactive phosphorus (SRP) concentrations increased from 101 μg l^− 1 in the mid 1960s to a maximum of 190 μg l^− 1 in 1989. In 2002, there was a step reduction in SRP concentration (average = 88 μg l^− 1 in 2002-2005), with further improvement in 2007-2009 (average = 49 μg l^− 1), due to the introduction of phosphorus stripping at sewage treatment works. Phosphorus and nitrate concentrations showed clear annual cycles, related to the timing of inputs from the catchment, and within-stream bioaccumulation and release. Annual depressions in silicon concentration each spring (due to diatom proliferation) reached a maximum between 1980 and 1991, (the period of maximum SRP concentration) indicating that algal biomass had increased within the river. The timing of these silicon depressions was closely related to temperature. Excess carbon dioxide partial pressures (EpCO₂) of 60 times atmospheric CO₂ were also observed through the winter periods from 1980 to 1992, when phosphorus concentration was greatest, indicating very high respiration rates due to microbial decomposition of this enhanced biomass. Declining phosphorus concentrations since 2002 reduced productivity and algal biomass in the summer, and EpCO₂ through the winter, indicating that sewage treatment improvements had improved riverine ecology. Algal blooms were limited by phosphorus, rather than silicon concentration. The value of long-term water quality data sets is discussed. The data from this monitoring programme are made freely available to the wider science community through the CEH data portal (http://gateway.ceh.ac.uk/).