Inorganic phosphorous availability and mobility in a manufactured soil.

Manufactured soils, created by combining various organic and inorganic waste materials and byproducts, may be tailored to specific applications, providing an alternative to the extraction of natural soils. It is important for them to be capable of supporting plant growth without the need for significant management or fertiliser applications, the over-application of which can have adverse environmental effects. We examined the dynamics of phosphorus (P) transformations within a manufactured soil and the implications for nutrient cycling. A freshly prepared manufactured soil (32.5 % composted green waste, 32.5 % composted bark, 25 % horticultural grit, and 10 % lignite clay) was studied over one year in temperature and moisture controlled mesocosms. Leachate was collected to achieve high-resolution monitoring of leached phosphate concentrations. Initially, leached dissolved inorganic phosphorus (DIP) concentrations were low (0.02 ± 0.01 mg P L-1), before increasing by 160 µg P L-1 d-1 over the first 42 days to 5.57 ± 1.23 mg P L-1. After reaching a maximum concentration, DIP concentrations remained relatively consistent, varying by only 1.67 mg P L-1 until day 270. The increase in leached DIP was likely driven by soil organic matter mineralisation and the cleavage of carbon­phosphorus bonds by the soil microbes to satisfy carbon demand with mineralogical influences, such as a decrease in apatite content, also contributing. Sorption and desorption from soil particles were the processes behind the P loss from the soil, which was followed by slow diffusion and eventual loss via leaching. The fertiliser application on phosphate dynamics resulted in increased DIP leaching. P concentrations observed in the manufactured soil were within the range considered sufficient to support plant growth. However, the mean leached phosphorus concentrations were higher than reported eutrophication thresholds suggesting that these soils may pose a risk to surface waters in their current form.

Uptake, accumulation and impact of antiretroviral and antiviral pharmaceutical compounds in lettuce.

While the contamination of agroecosystems with pharmaceutical compounds has been reported, the fate of these compounds, particularly uptake into plants remains unclear. This lack of environmental fate data is evident for a critical class of pharmaceuticals, the antivirals and antiretrovirals (ARVDs). Thus, this study evaluated the root uptake of the antiretroviral compounds nevirapine, lamivudine and efavirenz, and the antiviral compound oseltamivir in lettuce. The lettuce was hydroponically grown in a nutrient solution containing the four ARVD pharmaceutical mixture in the 1-100 µg L-1 concentration range. The measured bioaccumulation showed that efavirenz and lamivudine accumulated to the highest and lowest degree, at concentrations of 3463 ng g-1 and 691 ng g-1 respectively. The translocation factor between the root and leaf for nevirapine was greater than 1. The highest concentration of the pharmaceutical mixture had a physiological impact on the lettuce. Potential toxicity was evidenced by a statistically significant 34% (p = 0.04) mean reduction in root and leaf biomass in the 100 µg L-1 ARVD mix exposed lettuce, compared with the controls. This study advances knowledge of the fate of ARVDs in agroecosystems, in particular, plant root - ARVD interaction and the resulting potentially toxic effects on plants.

Developing the OECD 106 fate testing protocol for active pharmaceuticals in soil.

The ability to determine accurately the fate of APIs in soil is essential for rigorous risk assessment associated with wastewater reuse or biosolid recycling to land, particularly in lower income countries where water and fertiliser is scarce. Four APIs (naproxen, ofloxacin, propranolol and nevirapine) with wide ranging functionality were used as examples in the development of the OECD 106 soil partitioning and/or degradation study, with naproxen used to illustrate applying the full methodology. The data showed key methodological criteria require careful consideration and testing to generate accurate and consistent results. Only glass fibre membranes were suitable for all APIs, without unduly adsorbing APIs to their surface, thus effectively restricting the minimum practical pore size to 0.7 µm. Polypropylene plastic centrifuge tubes were shown to be suitable, with careful determination of recoveries. Direct injection liquid chromatography-mass spectrometry could reliably resolve all 4 APIs down to less than µg L-1 in soil solutions, although allowance for matrix effects via standard additions was required in some cases. Greatest analytical challenges were found for the highest molecular weight API with the greatest affinity for sorption to surfaces (ofloxacin). Key variables that can impact on partitioning such as solution pH and dissolved organic carbon concentrations were shown to vary within tests over time and should be accounted for.

Physico-chemical factors controlling the speciation of phosphorus in English and Welsh rivers.

Phosphorus is a finite resource essential for global food production. However, excessive loss to river systems from diffuse sources (typically agricultural) and point sources (e.g. waste water treatment works and industrial effluent) can lead to negative environmental impacts, including changes to diatom and invertebrate community structure. Current environmental quality standards for phosphorus in the UK have been based on reactive phosphorus, which is poorly defined and comprises an unknown proportion of soluble reactive phosphorus and chemically extractable particulate phosphorus. This research assesses the influencing factors that may control soluble reactive phosphorus concentrations in rivers, including dissolved iron, as well as partitioning processes associated with the presence of total suspended solids, and questions the reliability of the assumptions used when setting environmental quality standards. The extensive phosphorus speciation monitoring carried out across a wide geographic area of England and Wales shows that not all phosphorus as measured by the molybdenum blue method is either soluble or necessarily bioavailable, particularly at concentrations in the range in which the Environmental Quality Standard for 'Good' status (typically less than 100 µg P L-1) has been set. Phosphorus speciation can change due to physico-chemical processes which vary spatially and/or temporally, including precipitation with iron and partitioning with suspended solids.

Characterization of the Nairobi River catchment impact zone and occurrence of pharmaceuticals: Implications for an impact zone inclusive environmental risk assessment.

The largely uncontrolled release of active pharmaceuticals ingredients (APIs) within untreated wastewater discharged to waterbodies, associated with many rapidly urbanising centres is of growing concern owing to potential antimicrobial resistance, endocrine disruption and potential toxicity. A sampling campaign has been undertaken to assess the source, occurrence, magnitude and risk associated with APIs and other chemicals within the Nairobi/Athi river basin, in Kenya, East Africa. The catchment showed an extensive downstream impact zone estimated to extend 75 km, mostly, but not exclusively, derived from the direct discharge of untreated wastewater from the urban centre of Nairobi city. The exact extent of the downstream boundary of the Nairobi city impact zone was unclear owing to the inputs of untreated wastewater sources from the continuous urbanized areas along the river, which counteracted the natural attenuation caused by dilution and degradation. The most frequently detected APIs and chemicals were caffeine, carbamazepine, trimethoprim, nicotine, and sulfamethoxazole. Paracetamol, caffeine, sulfamethoxazole, and trimethoprim alone contributed 86% of the total amount of APIs determined along the Nairobi/Athi catchment. In addition to direct discharge of untreated domestic wastewater attributed to the informal settlements within the conurbation, other sources were linked to the industrial area in Nairobi City where drug formulation is known to occur, the Dandora landfill and veterinary medicines from upstream agriculture. It was shown that there was a possible environmental risk of API ecotoxicological effects beyond the end of the traditional impact zone defined by elevated biochemical oxygen demand concentrations; with metronidazole and sulfamethoxazole exhibiting the highest risk.

Biochar incorporation increased nitrogen and carbon retention in a waste-derived soil.

The synthesis of manufactured soils converts waste materials to value-added products, alleviating pressures on both waste disposal infrastructure and topsoils. For manufactured soils to be effective media for plant growth, they must retain and store plant-available nutrients, including nitrogen. In this study, biochar applications were tested for their ability to retain nitrogen in a soil manufactured from waste materials. A biochar, produced from horticultural green waste, was added to a manufactured soil at 2, 5 and 10 % (by weight), then maintained at 15 °C and irrigated with water (0.84 mL m-2 d-1) over 6 weeks. Total dissolved nitrogen concentrations in soil leachate decreased by 25.2, 30.6 and 44.0 % at biochar concentrations of 2, 5 and 10 %, respectively. Biochar also changed the proportions of each nitrogen-fraction in collected samples. Three mechanisms for biochar-induced nitrogen retention were possible: i) increased cation and anion exchange capacity of the substrate; ii) retention of molecules within the biochar pore spaces; iii) immobilisation of nitrogen through microbial utilisation of labile carbon further supported by increased soil moisture content, surface area, and pH. Dissolved organic carbon concentrations in leachate were reduced (-34.7 %, -28.9 %, and -16.7 %) in the substrate with 2, 5 and 10 % biochar additions, respectively. Fluorescein diacetate hydrolysis data showed increased microbial metabolic activity with biochar application (14.7 ±â€¯0.5, 25.4 ±â€¯5.3, 27.0 ±â€¯0.1, 46.1 ±â€¯6.1 µg FL g-1 h-1 for applications at 0, 2, 5, and 10 %, respectively), linking biochar addition to enhanced microbial activity. These data highlight the potential for biochar to suppress the long-term turnover of SOM and promote carbon sequestration, and a long-term sustainable growth substrate provided by the reuse of waste materials diverted from landfill.

Role of recent climate change on carbon sequestration in peatland systems.

This paper provides information on the impact of recent climate change on carbon sequestration in peatland systems in South West England. This is important because peatlands have the potential to sequester and hold large quantities of anthropogenically released CO2. This paper investigates whether there has been a reduction in the strength of carbon sinks in a valley mire and blanket bog, which occur on the limits of the biogeographical envelop for peatlands in Britain. Past rates of carbon accumulation were calculated from peat depth and the sequential analysis of peat age, bulk density and carbon content from cores taken from valley mire and blanket bog. At the valley mire site contemporary net ecosystem carbon balance (NECB) was calculated by measuring inputs to the peat body, via net primary productivity (NPP), of Sphagna. Losses of C from the peat body were calculated by measuring CH4, and aquatic carbon, calculated from catchment export of particulate and dissolved organic carbon. The study found similar mean rates of carbon accumulation since 1850 of 11.26 t ±â€¯0.68 t CO2e ha-1 yr-1 (307 g C m-2 yr-1) in valley mire and 11.77 t ±â€¯0.88 t CO2e ha-1 yr-1 (321 g C m-2 yr-1) in blanket bog. The mean present-day CO2 sequestration rate for Sphagna on valley mire was calculated to be 9.13 t ±â€¯0.98 t CO2e ha-1 yr-1 (249 g C m-2 yr-1). Both past and contemporary rates of CO2 sequestration were found to be at the maxima of those reported for temperate peatlands. NPP was found to vary according to microform with higher rates of carbon sequestration found in lawn and hummock microforms compared with pools. Our work suggests that recent changes in the climate appear to have had limited impact on the strength of peatland carbon sinks in South West England.

Impact of the wastewater-mixing zone on attenuation of pharmaceuticals in natural waters: Implications for an impact zone inclusive environmental risk assessment.

The direct discharge of untreated wastewater has been identified as an important source of environmental contamination by active pharmaceutical ingredients and other 'down-the-drain' chemicals in developing countries. It necessitates the development of an environmental risk assessment approach for the resulting impact zone. This study was designed to investigate the impact of low level of dilution (<10) on the natural attenuation processes of distribution and degradation within the impact zone. Dilution of the untreated wastewater resulted in increased desorption and corresponding environmental concentrations. The presence/absence of the microbial population in the batches affected the degree of sorption depending on the compound charge (i.e. positive or negative), highlighting an experimental technical bias. The degradation half-lives of acebutolol and diclofenac increased with increasing dilution and resulted in higher environmental persistence. The modelling of the biochemical oxygen demand (BOD) allowed an estimate of the temporal end boundary of the impact zone to be predicted as 24h. Therefore, it was concluded that most of the investigated compounds would persist beyond the end of the impact zone as defined by the return to environmental BOD concentrations. It is proposed that, within environmental risk assessment protocols, the impact zone should be considered as a semi-natural wastewater treatment area in such a way to allow the estimate of environmental concentrations of pharmaceuticals beyond its end.

The role of alkalinity in setting water quality metrics: phosphorus standards in United Kingdom rivers.

UK implementation of the European Union Water Framework Directive (for the 2015-2021 cycle) Ecological Status (ES) classification for river phosphorus is based on the calculation of reference conditions for reactive phosphorus (RP) using river alkalinity measurements. Underpinning this approach is that the alkalinity is primarily from rock weathering and is free of anthropogenic influences. However, the potential contribution of anthropogenic alkalinity needs to be considered and, if possible, quantified. In the rural South West River Basin District of England, 38 river sites were examined with respect to river alkalinity loads in order to test this consideration. At river base flow when RP can cause enhanced algal growth, 9 sites (24%) had effluent alkalinity contributions amounting to 25-49% of the total riverine alkalinity load, while 11 (29%) of the sites received ≥50% of their alkalinity load from effluent. When flows increased above base flow to Q95 flow at these 11 sites, catchment diffuse run-off became the largest load of alkalinity at 9 of the sites, and that at the Q95 flows, combined effluent and diffuse alkalinity loads contributed 68-100% of the total alkalinity load. Anthropogenic alkalinity is likely to be present in diffuse run-off, but it is difficult to apportion alkalinity loads between natural and contaminant sources. It is likely that diffuse loads of alkalinity will dominate on the annual timescales used to assess WFD compliance, even at sites where ground water alkalinity dominates at base river flows. In principle, inclusion of anthropogenic alkalinity in the calculation of ES boundary concentrations for RP may lead to a relaxation of the standards. In practice this may not follow. It is likely that at the river sites used initially to develop the algorithms now used for P standard setting, anthropogenic alkalinity was present, to varying and unknown degrees, and that this alkalinity would have influenced the measured and reference RP and biological metrics on which the P standards are based. Apart from RP, alkalinity is also used to underpin water quality metrics for additional chemical and biological parameters, and for this reason, understanding the complex factors determining river alkalinity loads should be an important task for water quality regulators.

Soil sterilisation methods for use in OECD 106: How effective are they?

Under many circumstances chemical risk assessments for pharmaceuticals and other substances are required to differentiate between 'loss' of a chemical from the aqueous phase as a result of abiotic (sorption or precipitation reactions) or biotic (biodegradation) processes. To distinguish only abiotic processes, it is necessary to work under sterile conditions. Reported methods include poisoning the soil with sodium azide, irradiation and autoclaving. However, a key aspect of any testing is the representativeness of the matrix and so any sterilisation procedure needs to ensure that the integrity of the sample is maintained, in particular particle size distribution, pH and organic carbon partitioning potential. A number of controlled laboratory experiments were performed on 3 different types of soil. Results indicated that none of the methods successfully sterilised the soils and some physico-chemical changes in soils were identified post-treatment. Autoclaving destroyed the soil structure, therefore potentially affecting its sorption behaviour and sodium azide changed the pH of the loam soil solution by 0.53 pH units. Gamma irradiation exhibited least disruption to the tested soils physico-chemical properties. It was therefore concluded that gamma irradiation was the best available method for sterilising soils in preparation for sorption-desorption experiments; however care needs to be taken with this method to ensure that microbial activity is absent, or quantified if present. The changes to soils after sterilisation varied depending on the individual soil properties, indicating that soils should be studied on a case-by-case basis.

Sorption of active pharmaceutical ingredients in untreated wastewater effluent and effect of dilution in freshwater: Implications for an "impact zone" environmental risk assessment approach.

Evidence of ecotoxicological effects of active pharmaceuticals ingredients (APIs) has increased research into their environmental fate. In low and low-middle income countries (LLMICs) the main source of APIs to surface waters is from discharge of untreated wastewater. Consequently, concentrations of APIs can be relatively high in the "impact zone" downstream of a discharge point. Little is known about the fate of APIs in these impact zones. In this laboratory scale investigation, the effect of successive dilution of synthetic untreated wastewater (dilution factor 1 to 10) on the distribution of APIs was studied. The sorption was consistent with the chemical properties of each compound: charge, lipophilicity, and structure. Dilution increased desorption of the basic and neutral APIs (up to 27.7%) and correlated with their lipophilicity (R2>0.980); the positive charge was of secondary importance. Anions did not significantly desorb (<10% loss). Increased concentrations of dissolved organic matter at dilutions of 8 and 10 times that of untreated wastewater coincided with lower dissolved API concentrations. The data showed a clear trend in the desorption process of APIs that may lead to higher exposure risk than anticipated. Therefore, it is suggested that these aspects should be accounted for in the development of dedicated environmental risk assessment approach for APIs in riverine impact zones of LLMICs countries.

Pharmaceuticals in soils of lower income countries: Physico-chemical fate and risks from wastewater irrigation.

Population growth, increasing affluence, and greater access to medicines have led to an increase in active pharmaceutical ingredients (APIs) entering sewerage networks. In areas with high wastewater reuse, residual quantities of APIs may enter soils via irrigation with treated, partially treated, or untreated wastewater and sludge. Wastewater used for irrigation is currently not included in chemical environmental risk assessments and requires further consideration in areas with high water reuse. This study critically assesses the contemporary understanding of the occurrence and fate of APIs in soils of low and lower-middle income countries (LLMIC) in order to contribute to the development of risk assessments for APIs in LLMIC. The physico-chemical properties of APIs and soils vary greatly globally, impacting on API fate, bioaccumulation and toxicity. The impact of pH, clay and organic matter on the fate of organic ionisable compounds is discussed in detail. This study highlights the occurrence and the partitioning and degradation coefficients for APIs in soil:porewater systems, API usage data in LLMICS and removal rates (where used) within sewage treatment plants as key areas where data are required in order to inform robust environmental risk assessment methodologies.

Orthophosphate-P in the nutrient impacted River Taw and its catchment (SW England) between 1990 and 2013.

Excess dissolved phosphorus (as orthophosphate-P) contributes to reduced river water quality within Europe and elsewhere. This study reports results from analysis of a 23 year (1990-2013) water quality dataset for orthophosphate-P in the rural Taw catchment (SW England). Orthophosphate-P and river flow relationships and temporal variations in orthophosphate-P concentrations indicate the significant contribution of sewage (across the catchment) and industrial effluent (upper R. Taw) to orthophosphate-P concentrations (up to 96%), particularly during the low flow summer months when maximum algal growth occurs. In contrast, concentrations of orthophosphate-P from diffuse sources within the catchment were more important (>80%) at highest river flows. The results from a 3 end-member mixing model incorporating effluent, groundwater and diffuse orthophosphate-P source terms suggested that sewage and/or industrial effluent contributes ≥50% of the orthophosphate-P load for 27-48% of the time across the catchment. The Water Framework Directive (WFD) Phase 2 standards for reactive phosphorus, introduced in 2015, showed the R. Taw to be generally classified as Poor to Moderate Ecological Status, with a Good Status occurring more frequently in the tributary rivers. Failure to achieve Good Ecological Status occurred even though, since the early-2000s, riverine orthophosphate-P concentrations have decreased (although the mechanism(s) responsible for this could not be identified). For the first time it has been demonstrated that sewage and industrial effluent sources of alkalinity to the river can give erroneous boundary concentrations of orthophosphate-P for WFD Ecological Status classification, the extent of which is dependent on the proportion of effluent alkalinity present. This is likely to be a European - wide issue which should be examined in more detail.

Bacterio-plankton transformation of diazepam and 2-amino-5-chlorobenzophenone in river waters.

Benzodiazepines are a large class of commonly-prescribed drugs used to treat a variety of clinical disorders. They have been shown to produce ecological effects at environmental concentrations, making understanding their fate in aquatic environments very important. In this study, uptake and biotransformations by riverine bacterio-plankton of the benzodiazepine, diazepam, and 2-amino-5-chlorobenzophenone, ACB (a photo-degradation product of diazepam and several other benzodiazepines), were investigated using batch microcosm incubations. These were conducted using water and bacterio-plankton populations from contrasting river catchments (Tamar and Mersey, UK), both in the presence and absence of a peptide, added as an alternative organic substrate. Incubations lasted 21 days, reflecting the expected water residence time in the catchments. In River Tamar water, 36% of diazepam (p < 0.001) was removed when the peptide was absent. In contrast, there was no removal of diazepam when the peptide was added, although the peptide itself was consumed. For ACB, 61% was removed in the absence of the peptide, and 84% in its presence (p < 0.001 in both cases). In River Mersey water, diazepam removal did not occur in the presence or absence of the peptide, with the latter again consumed, while ACB removal decreased from 44 to 22% with the peptide present. This suggests that bacterio-plankton from the Mersey water degraded the peptide in preference to both diazepam and ACB. Biotransformation products were not detected in any of the samples analysed but a significant increase in ammonium concentration (p < 0.038) was measured in incubations with ACB, confirming mineralization of the amine substituent. Sequential inoculation and incubation of Mersey and Tamar microcosms, for 5 periods of 21 days each, did not produce any evidence of increased ability of the microbial community to remove ACB, suggesting that an indigenous consortium was probably responsible for its metabolism. As ACB degradation was consistent, we propose that the aquatic photo-degradation of diazepam to ACB, followed by mineralization of ACB, is a primary removal pathway for these emerging contaminants. As ACB is photo-produced by several benzodiazepines, this pathway should be relevant for the removal of other benzodiazepines that enter the freshwater environment.

Temporal variability in nutrient concentrations and loads in the River Tamar and its catchment (SW England) between 1974 and 2004.

This study reports the results from the analyses of a 30-year (1974-2004) river water quality monitoring dataset for NO x -N (NO3-N + NO2-N), NH4-N, PO4-P and SiO2-Si at the tidal limit of the River Tamar (SW England), an agriculturally dominated and sparsely populated catchment. Annual mean concentrations of NH4-N, PO4-P and SiO2-Si were similar to other rural UK rivers, while annual mean concentrations of NO x -N were clearly lower. Estimated values for the 1940s were much lower than for those of post-1974, at least for NO3-N and PO4-P. Flow-weighted mean concentrations of PO4-P decreased by approximately 60 % between 1974 and 2004, although this change cannot be unequivocally ascribed to either PO4-P stripping from sewage treatment work effluents or reductions in phosphate fertiliser applications. Lower-resolution sampling (to once per month) in the late 1990s may also have led to the apparent decline; a similar trend was also seen for NH4-N. There were no temporal trends in the mean concentrations of NO x -N, emphasising the continuing difficulty in controlling diffuse pollution from agriculture. Concentrations of SiO2-Si and NO x -N were significantly and positively correlated with river flows ≤15 m(3) s(-1), showing that diffuse inputs from the catchment were important, particularly during the wet winter periods. In contrast, concentrations of PO4-P and NH4-N did not correlate across any flow window, despite the apparent importance of diffuse inputs for these constituents. This observation, coupled with the absence of a seasonal (monthly) cycle for these nutrients, indicates that, for PO4-P and NH4-N, there were no dominant sources and/or both undergo extensive within-catchment processing. Analyses of nutrient fluxes reveal net losses for NO3-N and SiO2-Si during the non-winter months; for NO3-N, this may be due to denitrification. Areal fluxes of NO x -N from the catchment were towards the higher end of the range for the UK, while NH4-N and PO4-P were closer to the lower end of the ranges for these nutrients. These data, taken together with information on sestonic chlorophyll a, suggest that water quality in the lower River Tamar is satisfactory with respect to nutrients. Analyses of these monitoring data, which were collected at considerable logistical and monetary cost, have revealed unique insights into the environmental behaviour of key nutrients within the Tamar catchment over a 30-year period.

A high resolution temporal study of phytoplankton bloom dynamics in the eutrophic Taw Estuary (SW England).

The Taw Estuary (SW England) is eutrophic as a result of enhanced nutrient inputs from its catchment. However, factors influencing the timing and extent of phytoplankton bloom formation are not fully understood in this system. In this study, high resolution chemical and biological sampling was undertaken in late-winter/spring and summer 2008 in order to gain further insights into bloom dynamics in the Taw Estuary. Temporal variations in chlorophyll a maxima in the upper and middle estuary during summer were controlled by river flow and tidal amplitude, with nutrient limitation probably less important. Concentrations of chlorophyll a were highest during low river flow and neap tides. Increased river flows advected the chlorophyll maximum to the outer estuary, and under highest river discharges, chlorophyll a concentrations were further reduced. This feature was even more pronounced when spring tides coincided with high flows. The main bloom species were the diatoms Asterionellopsis glacialis and Thalassiosira guillardii. Using two multivariate statistical techniques in combination, five distinct physical and biogeochemical states in the Taw estuarine waters were identified. These states can be summarised as: A(1), high chlorophyll a, high temperature, long residence times, nutrient depletion; A(2), strong coastal water influence; B(1), decreasing chlorophyll a, increasing river flow and/or spring tides; B(2), transitional between states A(1) and B(3); B(3), high river flow. It was thus possible to differentiate between contrasting environmental conditions that were either beneficial or detrimental for the development of algal blooms. A conceptual model of diatom - dominated primary production for the Taw Estuary is proposed which describes how physical controls (river flow, tidal state) moderate plankton biomass production in the upper and mid - estuarine regions.

Temporal variability in dynamic and colloidal metal fractions determined by high resolution in situ measurements in a UK estuary.

In recent environmental legislation, such as the Water Framework Directive in the European Union (WFD, 2000/60/EC), the importance of metal speciation and biological availability is acknowledged, although analytical challenges remain. In this study, the Voltammetric In situ Profiler (VIP) was used for high temporal resolution in situ metal speciation measurements in estuarine waters. This instrument simultaneously determines Cd, Cu and Pb species within a size range (ca. <4 nm) that is highly relevant for uptake by organisms. The colloidal metal fraction can be quantified through a combination of VIP measurements and analyses of total dissolved metal concentrations. VIP systems were deployed over tidal cycles in a seasonal study of metal speciation in the Fal Estuary, southwest England. Total dissolved concentrations were 4.97-315 nM Cu, 0.13-8.53 nM Cd and 0.35-5.75 nM Pb. High proportions of Pb (77±17%) and Cu (60±25%) were present as colloids, which constituted a less important fraction for Cd (37±30%). The study elucidated variations in the potentially toxic metal fraction related to river flow, complexation by organic ligands and exchanges between dissolved and colloidal phases and the sediment. Based on published toxicity data, the bioavailable Cu concentrations (1.7-190 nM) in this estuary are likely to severely compromise the ecosystem structure and functioning with respect to species diversity and recruitment of juveniles. The study illustrates the importance of in situ speciation studies at high resolution in pursuit of a better understanding of metal (bio)geochemistry in dynamic coastal systems.

Dissolved silver in European estuarine and coastal waters.

Silver is one of the most toxic elements for the marine microbial and invertebrate community. However, little is known about the distribution and behaviour of dissolved silver in marine systems. This paper reports data on dissolved and sediment-associated silver in European estuaries and coastal waters which have been impacted to different extents by past and present anthropogenic inputs. This is the first extended dataset for dissolved silver in European marine waters. Lowest dissolved silver concentrations were observed in the Gullmar Fjord, Sweden (8.9 +/- 2.9 pM; x +/- 1sigma), the Tamar Estuary, UK (9.7 +/- 6.2 pM), the Fal Estuary, UK (20.6 +/- 8.3 pM), and the Adriatic Sea (21.2 +/- 6.8 pM). Enhanced silver concentrations were observed in Atlantic coastal waters receiving untreated sewage effluent from the city of A Coruna, Spain (243 +/- 195 pM), and in the mine-impacted Restronguet Creek, UK (91 +/- 71 pM). Anthropogenic wastewater inputs were a source of dissolved silver in the regions studied, with the exception of the Gullmar Fjord. Remobilisation of dissolved silver from historically contaminated sediments, resulting from acid mine drainage or sewage inputs, provided an additional source of dissolved silver to the estuaries. The ranges in the log particle-water partition coefficient (K(d)) values of 5-6 were similar for the Tamar and Mero estuaries and agreed with reported values for other estuaries. These high K(d) values indicate the particle reactive nature of silver with oxic sediments. In contrast, low K(d) values (1.4-2.7) were observed in the Fal system, which may have been due to enhanced benthic inputs of dissolved silver coupled to limited scavenging of silver on to sediments rich in Fe oxide.

The use of monitoring data for identifying factors influencing phytoplankton bloom dynamics in the eutrophic Taw Estuary, SW England.

Using the Taw Estuary as an example, data routinely collected by the Environment Agency for England and Wales over the period 1990-2004 were interrogated to identify the drivers of excessive algal growth. The estuary was highly productive with chlorophyll concentrations regularly exceeding 100 microg L(-1), mostly during periods of low freshwater input from the River Taw when estuarine water residence times were longest. However, algal growth in mid estuary was often inhibited by ammonia inputs from the adjacent sewage treatment works. The reported approach demonstrates the value of applying conventional statistical analyses in a structured way to existing monitoring data and is recommended as a useful tool for the rapid assessment of eutrophication. However, future estuarine monitoring should include the collection of dissolved organic nutrient data and targeted high temporal resolution data because the drivers of eutrophication are complex and often very specific to a particular estuary.

Characterisation and quantification of organic phosphorus and organic nitrogen components in aquatic systems: a review.

This review provides a critical assessment of knowledge regarding the determination of organic phosphorus (OP) and organic nitrogen (ON) in aquatic systems, with an emphasis on biogeochemical considerations and analytical challenges. A general background on organic phosphorus and organic nitrogen precedes a discussion of sample collection, extraction, treatment/conditioning and preconcentration of organic phosphorus/nitrogen from sediments, including suspended particulate matter, and waters, including sediment porewaters. This is followed by sections on the determination of organic phosphorus/nitrogen components. Key techniques covered for organic phosphorus components are molecular spectrometry, atomic spectrometry and enzymatic methods. For nitrogen the focus is on the measurement of total organic nitrogen concentrations by carbon hydrogen nitrogen analysis and high temperature combustion, and organic nitrogen components by gas chromatography, high-performance liquid chromatography, gel electrophoresis, mass spectrometry, nuclear magnetic resonance spectrometry, X-ray techniques and enzymatic methods. Finally future trends and needs are discussed and recommendations made.