Defining the sources of low-flow phosphorus transfers in complex catchments

Nutrient transfers from the land to rivers have the potential to cause persistent eutrophic impacts at low flows even though the transfers may constitute a minor percentage of total annual fluxes. In rural catchments, the contribution from agricultural soils during storm events can be particularly large and untangling the relative contributions from multiple sources that vary in time and space is especially problematic. In this study, the potential for domestic septic tank system pollution during low flows was investigated in 3 small catchments (3 to 5 km(2)) using an integrated series of methods. These included septic system surveys, continuous (10 min) total phosphorus (TP) monitoring at the outlet of each catchment, repeated low-flow water quality surveys in sub-catchments upstream of the catchment outlets and single day river-walk water quality surveys. A series of faecal matter and grey-water fingerprinting techniques were also employed. These included determining sterol ratios in stream sediments, monitoring the presence of proteins, E. coli and enterococci bacterial signatures and boron. The total density and density of poorly maintained septic systems mirrored the magnitude of frequent TP concentrations in the catchments although this relationship was less apparent in the nested sub-catchments. The exception was possibly related to the simple hydraulics in one particular catchment and indicated temporary effluent attenuation in the other catchments. Repeated low-flow and river-walk water quality surveys highlighted discrete areas and reaches where stepped changes in nutrient concentration occurred. Bio-chemical fingerprinting showed that between 7% and 27% of sediments were contaminated with human faecal material and correlation matrices indicated that, at least during low flows, P fractions were positively correlated with some markers of faecal and grey-water contamination.     

Trends in hydrometeorological conditions and stream water organic carbon in boreal forested catchments

Temporal trends in stream water total organic carbon (TOC) concentration and export were studied in 8 forested headwater catchments situated in eastern Finland. The Seasonal Kendall test was conducted to identify the trends and a mixed model regression analysis was used to describe how catchment characteristics and hydrometeorological variables (e.g. precipitation, air and stream water temperatures, and atmospheric deposition) related to the variation in the concentration and export of stream water TOC. The 8 catchments varied in size from 29 to 494 ha and in the proportion of peatland they contained, from 8 to 70%. Runoff and TOC concentration were monitored for 15-29 years (1979-2006). Trends and variation in TOC levels were analysed from annual and seasonal time series. Mean annual TOC concentration increased significantly in seven of the eight catchments. The trends were the strongest in spring and most apparent during the last decade of the study period. The slopes of the trends were generally smaller than the variation in TOC concentration between years and seasons and between catchments. The annual TOC export showed no clear trends and values were largely determined by the temporal variability in runoff. Annual runoff showed a decreasing trend in two of the eight catchments. Mean annual air and stream water temperatures showed increasing trends, most clearly seen in the summer and autumn series. According to our modeling results, stream water temperature, precipitation and peatland percentage were the most important variables explaining annual and most seasonal TOC concentrations. The atmospheric deposition of SO₄, NH₄, and NO₃ decreased significantly over the study period, but no significant link with TOC concentration was found. Precipitation was the main hydrometeorological driver of the TOC export. We concluded that stream water TOC concentrations and exports are mainly driven by catchment characteristics and hydrometeorological factors rather than trends in atmospheric acid deposition.     

Agriculture-induced increase in nitrate concentrations in stream waters of a large Mediterranean catchment over 25 years (1981–2005)

Anthropogenic activities influence past and present nitrate levels recorded in European stream waters, posing a threat to aquatic biota and human beings. Scarce information on temporal trends of nitrate concentration and its causes is available for Mediterranean catchments. This study presents the evolution of nitrate concentrations over 25 years in stream waters of the Ebro River Basin (Spain), a large Mediterranean catchment involving 85,566 km². Nitrate concentration increased with time in 46% of the 65 sites involved in the study. Agricultural cover of 30 hydrologically independent sub-catchments was the main land use related to nitrate concentration (R² = 0.69). Throughout the 25 year-period, the sites showing increased nitrate concentrations with time (trend sites) also presented an enhanced influence of agricultural cover on nitrate concentrations along the time frame of the study. As a result of these temporal changes, at the end of the studied period nitrate concentrations in stream waters responded similarly to agricultural cover in both trend and non-trend sites, showing non significant differences in the slope of the resultant regression models. At this time, agricultural cover explained 82% of the variability found in nitrate levels. If these trends remain unchanged, in 2015 many of the water bodies considered in this study would not comply with the requirements of the European Union Water Framework Directive (WFD). Therefore management decisions, mainly associated to agricultural practices, should be implemented as soon as possible at the catchment level to meet WFD objectives.     

The relative contribution of sewage and diffuse phosphorus sources in the River Avon catchment, southern England: implications for nutrient management

In order to effectively manage nutrient river load reductions and target remediation strategies, it is important to determine the relative contributions of diffuse and point sources across the river catchment. This study used a geographical information system (GIS) to apply phosphorus (P) export coefficients (obtained from the literature) to 58 water quality monitoring sites across a large, urbanised, mixed land use catchment, typical of southern lowland England (the River Avon, Warwickshire, UK). These coefficients were used to estimate the annual P load at each monitoring site, and also the relative contribution of point source (from sewage treatment works (STW)) and diffuse input (from both livestock and agricultural land use). The estimated annual P loads showed very close agreement (r2=0.98) with the measured total phosphorus (TP) loads. Sites with the highest proportion of P derived from STW had the highest TP concentrations and loads, and also had greater variations between seasons, with elevated P concentrations occurring during the summer months. The GIS model was re-run to determine the effect of an 80% reduction in P output from STW serving over 10,000 people, thereby assessing the effect of implementing the European Union's Urban Waste Water Treatment Directive (UWWTD). The exported TP load was reduced by 52%, but the sites with the highest TP concentrations were still those with the highest proportion of P derived from STW. The GIS model was re-run to estimate the impact of 80% P reductions at a further 11 STW of varying sizes. This reduced the total TP load by only 29 tonnes year-1, but greatly reduced the P concentrations in many highly nutrient contaminated tributaries. The number of sites with P concentrations greater than 1 mg l-1 was cut from 15 (before UWWTD implementation) to 2. These findings suggest that after UWWTD implementation, resources should focus on introducing tertiary sewage treatment at the remaining large STW, before targeting diffuse inputs. This conclusion is also likely to apply to other lowland river catchments in southern England, most of which have similar population densities to the River Avon.     

The 20th century whole-basin trophic history of an inter-drumlin lake in an agricultural catchment

Eight 1-m sediment cores were extracted from across the basin of Friary Lough, a 5.4-ha eutrophic lake in a wholly grassland agricultural catchment in Co. Tyrone, Northern Ireland. Sedimentary TP, diatom inferred TP, Ca, Na, Fe, Mn, loss-on-ignition (LOI), dry weight and density were determined in the core profiles. Core dating and correlation gave a 210Pb, 137Cs and 241Am chronology from 1906 to 1995 and enabled a whole-basin estimate of chemical and sediment accumulation rate over the 20th Century. The major changes for all parameters occurred after c. 1946. Sediment accumulation rate was most influenced by organic matter accumulations, probably of planktonic origin, and increasing after c. 1946. Inorganic sediment accumulation rate was found to be largely unchanging through the century at 10 t km(-2) yr(-1) when expressed as catchment exports. All chemical accumulation rate changes occurred after c. 1946. Total phosphorus accumulation rate, however, was found to be the only chemical to be increasing throughout the epilimnion and hypolimnion areas of the sedimentary basin at an average of 22.5 mg m(-2) yr(-1) between 1946 and 1995. The other chemical parameters showed increasing accumulation rates after c. 1946 in the epilimnion part of the basin only. Interpreted in terms of whole-basin sedimentation and catchment export processes over time, it is suggested that diffuse TP inputs are independent of sediment inputs. This corresponds to hydrochemical models that suggest soluble P as the primary fraction that is lost from grassland catchments. The increase in sedimentary TP accumulation rate, and DI-TP concentration, are also explained with regard to current models that suggest increases in runoff P concentrations from elevated soil P concentrations. Increases in eplimnion chemical and sediment accumulation rate after c. 1946 may be due to local erosion that has limited impact on lake basin sedimentation.     

Quantifying the effects of forestry practices on the recovery of upland streams and lochs from acidification

Trends in long-term chemistry data are presented for 37 acidified upland streams and lochs, located in four areas (A, B, C and D) across Scotland, to provide a comparison between recovery rates of moorland catchments and forest catchments at different stages of the management cycle. For all sites, non-marine sulfate (nm-SO(4)) showed a significant decline in annual median concentrations, the greatest decline being in streams draining felled catchments, which showed a 50% greater decline than catchments with moorland or young, aggrading forests. A similar pattern was found for chloride (Cl) concentrations in Area C, which reflected the reduced interception of sea-salt aerosols following clearfelling. However, high elevation moorland sites in Area D also revealed significant declines in Cl while trends in aggrading forest sites in this area were insignificant. Alkalinity (ALK) and pH increased more at sites where felling had taken place than at moorland or young forest sites while aggrading forest catchments appeared to be most resistant to changes in pH and ALK. Associated with these acid-base changes was a corresponding decline in labile aluminium (Al-L) concentrations. The pattern of nitrate (NO(3)) change was especially affected by the timing of felling in forested catchments. Large negative trends in NO(3) at stream sites were associated with felling during the early part of the study period. This downward trend was further enhanced as NO(3) concentrations fell below pre-felling levels as the second rotation crop became established. Few forest sites showed significant increases in NO(3) due to felling in the latter part of the study period. Most moorland loch sites showed a small but significant increase in NO(3,) probably in response to similar increases in N deposition and/or climatic impacts. Dissolved organic carbon (DOC) increased significantly at both forest and moorland sites, however, the extent of these increasing trends appeared to be positively correlated with absolute DOC concentrations. Despite the complex response of streams and lochs during the various stages of the forest cycle, especially for NO(3), both forest and moorland catchments showed generally similar and rapid responses to reductions in S deposition. Nevertheless, forested sites are still more acid and have higher concentrations of toxic forms of Al than moorland sites. Although the proposed emission reductions in Europe are likely to result in a continuing decline in S and N loadings to catchments, the continuing policy of planting second rotation forests in these acidified catchments may, in the long-term, delay or halt chemical and biological recovery. However, in the short-term, any increase in the uptake of N deposition by aggrading forests should help to counteract the acidifying effects of a small increase in the interception of S and N compounds.     

Modelling of phosphorus inputs to rivers from diffuse and point sources

The difference in timing of point and diffuse phosphorus (P) delivery to a river produces clear differences in the P concentration-flow relationship. Point inputs decrease in concentration with increasing river flow, due to dilution of a relatively constant input, whereas diffuse (non-point) load usually increases with river flow. This study developed a simple model, based on this fundamental difference, which allowed point and diffuse inputs to be quantified by modelling their contribution to river P concentration as a power-law function of flow. The relationships between total phosphorus (TP) concentration and river flow were investigated for three contrasting UK river catchments; the Swale (Yorkshire), the Frome (Dorset) and the Avon (Warwickshire). A load apportionment model was fitted to this empirical data to give estimates of point and diffuse load inputs at each monitoring site, at high temporal resolution. The model produced TP source apportionments that were similar to those derived from an export coefficient approach. For many diffuse-dominated sites within this study (with up to 75% of the annual TP load derived from diffuse sources), the model showed that reductions of point inputs would be most effective in order to reduce eutrophication risk, due to point source dominance during the plant and algae growing period. This modelling approach should provide simple, robust and rapid TP source apportionment from most concentration-flow datasets. It does not require GIS, information on land use, catchment size, population or livestock density, and could provide a valuable and versatile tool to catchment managers for determining suitable river mitigation options.     

Export of dissolved organic matter in relation to land use along a European climatic gradient

The terrestrial export of dissolved organic matter (DOM) is associated with climate, vegetation and land use, and thus is under the influence of climatic variability and human interference with terrestrial ecosystems, their soils and hydrological cycles. We present a data-set including catchments from four areas covering the major climate and land use gradients within Europe: a forested boreal zone (Finland), a temperate agricultural area (Denmark), a wet and temperate mountain region in Wales, and a warm Mediterranean catchment draining into the Gulf of Lyon. In all study areas, DOC (dissolved organic carbon) was a major fraction of DOM, with much lower proportions of DON (dissolved organic nitrogen) and DOP (dissolved organic phosphorus). A south-north gradient with highest DOC concentrations and export in the northernmost catchments was recorded: DOC concentrations and loads were highest in Finland and lowest in France. These relationships indicate that DOC concentrations/export are controlled by several factors including wetland and forest cover, precipitation and hydrological processes. DON concentrations and loads were highest in the Danish catchments and lowest in the French catchments. In Wales and Finland, DON concentrations increased with the increasing proportion of agricultural land in the catchment, whereas in Denmark and France no such relationship was found. DOP concentrations and loads were low compared to DOC and DON. The highest DOP concentrations and loads were recorded in catchments with a high extent of agricultural land, large urban areas or a high population density, reflecting the influence of human impact on DOP loads.     

Dissolved and particulate nutrient export from rural catchments: a case study from Luxembourg

Nutrient enrichment of freshwaters continues to be one of the most serious problems facing the management of surface waters. Effective remediation/conservation measures require accurate qualitative and quantitative knowledge of nutrient sources, transport mechanisms, transformations and annual dynamics of different nitrogen (N) and phosphorus (P) forms. In this paper, nitrate (NO3-N), soluble reactive phosphorus (SRP) and total phosphorus (TP) concentrations and loads are presented for two adjacent rural basins of 306 km2 and 424 km2, and for five sub-basins differing in size (between 1 km2 and 33 km2), land use (extent of forest cover between 20% and 93%) and household pressure (from 0 to 40 people/km2) with the aim of studying the influence of land use and catchment size on nutrient exports. The studied catchments are all situated on Devonian schistous substrates in the Ardennes region (Belgium-Luxembourg), and therefore have similar hydrological regimes. As the study period could not be the same for all basins, annual export coefficients were corrected with the 25 years normalized discharge of the Sure River: two regression analyses (for dry and humid periods) relating monthly nutrient loads to monthly runoff were used to determine correction factors to be applied to each parameter and each basin. This procedure allows for the comparing annual export coefficients from basins sampled in different years. Results show a marked seasonal response and a large variability of NO3-N export loads between forested (4 kg N ha-1 year-1), agricultural (27-33 kg N ha-1 year-1) and mixed catchments (17-22 kg N ha-1 year-1). For SRP and TP, no significant agricultural impact was found. Land and bank erosion control the total P massflow in the studied catchments (0.4-1.3 kg P ha-1 year-1), which is mostly in a particulate form, detached and transported during storm events. Soluble reactive P fluxes ranged between 10% and 30% of the TP mass, depending on the importance of point sources in the basins studied. No relation was found between the size of the basins and the export of nitrate, SRP or TP. Nutrient export, specially for NO3-N and TP, shows significant inter-annual variations, closely linked to inter-annual discharge variations. Flow and load frequency data analysis confirm this association for all the basins on an annual basis. Seasonal or storm specific fluxes strongly deviate from their annual values.     

A comparison of SWAT, HSPF and SHETRAN/GOPC for modelling phosphorus export from three catchments in Ireland

Recent extensive water quality surveys in Ireland revealed that diffuse phosphorus (P) pollution originating from agricultural land and transported by runoff and subsurface flows is the primary cause of the deterioration of surface water quality. P transport from land to water can be described by mathematical models that vary in modelling approach, complexity and scale (plot, field and catchment). Here, three mathematical models (soil water and analysis tools (SWAT), hydrological simulation program-FORTRAN (HSPF) and système hydrologique Européen TRANsport (SHETRAN)/grid oriented phosphorus component (GOPC)) of diffuse P pollution have been tested in three Irish catchments to explore their suitability in Irish conditions for future use in implementing the European Water Framework Directive. After calibrating the models, their daily flows and total phosphorus (TP) exports are compared and assessed. The HSPF model was the best at simulating the mean daily discharge while SWAT gave the best calibration results for daily TP loads. Annual TP exports for the three models and for two empirical models were compared with measured data. No single model is consistently better in estimating the annual TP export for all three catchments.     

Trends in stream water quality in Environmental Change Network upland catchments: the first 5 years

Hydrochemical data from catchment streams at three Environmental Change Network (ECN) upland catchments in north-east Scotland, south-east Scotland and northern England have been subjected to statistical analysis to separate the components due to long-term trend, season and flow. The relative variances due to each are presented for pH, Ca, SO4-S, NO3-N, DOC and Cl. Long-term trends have been identified with increases in concentration for NO3-N and DOC, decreases in SO4-S concentrations, along with short-term seasonal fluctuations. Application of this trend technique has allowed the detection of changes and contributed to an improved understanding of catchment behaviour.     

Stream water hydrochemistry as an indicator of carbon flow paths in Finnish peatland catchments during a spring snowmelt event

Extreme hydrological events are known to contribute significantly to total annual carbon export, the largest of which in Arctic and boreal catchments is spring snowmelt. Whilst previous work has quantified the export of carbon during snowmelt, the source of the carbon remains unclear. Here we use cation hydrochemistry to trace the primary flowpaths which govern the export of carbon during the snowmelt period; specifically we aim to examine the importance of snowpack meltwater to catchment carbon export. The study was carried out in two forested peatland (drained and undrained) catchments in Eastern Finland. Both catchments were characterised by base-poor stream water chemistry, with cation concentrations generally decreasing in response to increasing discharge. Streamflow during the snowmelt period was best described as a mixture of three sources: pre-event water, snowpack meltwater and a third dilute component we attribute to the upper snow layer which was chemically similar to recent precipitation. Over the study period, pre-event water contributed 32% and 43% of the total stream runoff in Välipuro (undrained) and Suopuro (drained), respectively. The results also suggest a greater near-surface throughflow component in Suopuro, the drained catchment, prior to snowmelt. CO₂ and DOC concentrations correlated positively with cation concentrations in both catchments indicating a common, peat/groundwater flowpath. CH₄ concentrations were significantly higher in the drained catchment and appeared to be transported in near-surface throughflow. Meltwater from the snowpack represented an important source of stream water CO₂ in both catchments, contributing up to 49% of total downstream CO₂ export during the study period. We conclude that the snowpack represents a potentially important, and often overlooked, transient carbon store in boreal snow-covered catchments.     

The effect of beaver ponds on the nonpoint source water quality of a stream in Southwestern Wyoming

Currant Creek, a second order stream in southwestern Wyoming, has three large complexes of beaver ponds midway along its 32 km length. To determine whether these ponds improve the quality of water flowing through them, during spring and summer of 1984 and 1985 water samples were taken upstream from, within, and downstream from the pond complexes. During periods of high flow (i.e. spring runoff), concentrations of suspended solids (SS), total phosphorus (TP), sodium hydroxide-extractable phosphorus (NaOH-P, an index of biologically available P) and total Kjeldahl nitrogen (TKN) were reduced in water flowing through the beaver ponds. During low flow, beaver ponds had less effect on these parameters. Concentrations of nitrate nitrogen (NO₃-N) were reduced during both high and low flows, while concentrations of ortho-phosphate (ortho-P) did not appear to be affected by beaver ponds. Ammonia nitrogen almost always was at the limit of detection. Regression of NaOH-P versus [SS plus ortho-P] suggested that the primary source of NaOH-P was SS. In general, SS explained a large portion of the variation in TP, TKN, and NaOH-P, and often ortho-P was significantly correlated to TP. The increase in the concentration of most parameters below the area with dam complexes appears to reflect input from bank and channel erosion, and export of SS, TP, TKN and NO₃-N from beaver dam complexes was calculated to be less than that from stream sections above or below the dams. Thus the location of dams should be considered before using them to try and improve water quality. The apparent importance of bank and channel erosion as the primary source of nutrients to Currant Creek contrasts with many watersheds in agricultural areas.     

Microbial water pollution: A screening tool for initial catchment-scale assessment and source apportionment

The European Union Water Framework Directive requires that Management Plans are developed for individual River Basin Districts. From the point of view of faecal indicator organisms (FIOs), there is a critical need for screening tools that can provide a rapid assessment of the likely FIO concentrations and fluxes within catchments under base- and high-flow conditions, and of the balance (‘source apportionment’) between agriculture- and sewage-derived sources. Accordingly, the present paper reports on: (1) the development of preliminary generic models, using water quality and land cover data from previous UK catchment studies for assessing FIO concentrations, fluxes and source apportionment within catchments during the summer bathing season; (2) the calibration of national land use data, against data previously used in the models; and (3) provisional FIO concentration and source-apportionment assessments for England and Wales. The models clearly highlighted the crucial importance of high-flow conditions for the flux of FIOs within catchments. At high flow, improved grassland (and associated livestock) was the key FIO source; FIO loadings derived from catchments with high proportions of improved grassland were shown to be as high as from urbanised catchments; and in many rural catchments, especially in NW and SW England and Wales, which are important areas of lowland livestock (especially dairy) farming, ≥ 40% of FIOs was assessed to be derived from agricultural sources. In contrast, under base-flow conditions, when there was little or no runoff from agricultural land, urban (i.e. sewerage-related) sources were assessed to dominate, and even in rural areas the majority of FIOs were attributed to urban sources. The results of the study demonstrate the potential of this type of approach, particularly in light of climate change and the likelihood of more high-flow events, in underpinning informed policy development and prioritisation of investment.     

Spatial heterogeneity of the spring flood acid pulse in a boreal stream network

Spatial and temporal patterns in streamwater acidity are ecologically important, but difficult to measure in parallel. Here we present the spatial distribution of streamwater chemistry relevant to acidity from 60 stream sites distributed throughout a 67 km² boreal catchment, sampled during a period of winter baseflow (high pH) and during a spring flood episode (low pH). Sites were grouped based on pH level and pH change from winter baseflow to spring flood. The site attributes of each pH group were then assessed in terms of both stream chemistry and subcatchment landscape characteristics. Winter baseflow pH was high throughout most of the stream network (median pH 6.4), but during the spring flood episode stream sites experienced declines in pH ranging from 0-1.6 pH units, resulting in pH ranging from 4.3-6.3. Spring flood pH was highest in larger, lower altitude catchments underlain by fine sorted sediments, and lowest in small, higher altitude catchments with a mixture of peat wetlands and forested till. Wetland-dominated headwater catchments had low but stable pH, while the spring flood pH drop was largest in a group of catchments of intermediate size which contained well-developed coniferous forest and a moderate proportion of peat wetlands. There was a trend with distance downstream of higher pH, acid neutralizing capacity (ANC) and base cation concentrations together with lower dissolved organic carbon (DOC, strongly negatively correlated with pH). This apparent scale-dependence of stream chemistry could be explained by a number of environmental factors which vary predictably with altitude, catchment area and distance downstream—most notably, a shift in surficial sediment type from unsorted till and peat wetlands to fine sorted sediments at lower altitudes in this catchment. As a result of the combination of spatial heterogeneity in landscape characteristics and scale-related processes, boreal catchments like this one can be expected to experience high spatial variability both in terms of chemistry at any given point in time, and in the change experienced during high discharge episodes. Although chemistry patterns showed associations with landscape characteristics, considerable additional variability remained, suggesting that the modeling of dynamic stream chemistry from map parameters will continue to present a challenge.     

Modelling through-soil transport of phosphorus to surface waters from livestock agriculture at the field and catchment scale

A model of phosphorus (P) losses in a small dairy farm catchment has been set up based on a linkage of weather-driven field-scale simulations using an adaptation of the MACRO model. Phosphorus deposition, both in faeces from grazing livestock in summer and in slurry spread in winter, has been represented. MACRO simulations with both forms of P deposition had been calibrated and tested at the individual field scale in previous studies. The main contaminant transport mechanism considered at both field and catchment scales is P sorbed onto mobile colloidal faeces particles, which move through the soil by macropore flow. Phosphorus moves readily through soil to field drains under wet conditions when macropores are water-filled, but in dry soil the P carrying colloids become trapped so losses remain at a low level. In the catchment study, a dairy farm is assumed to be composed of fields linked by a linear system of ditches which discharge into a single river channel. Results from linked simulations showed reasonable fits to values of catchment outflow P concentrations measured at infrequent intervals. High simulated outflow P concentrations occurred at similar times of year to high measured values, with some high loss periods during the summer grazing season and some during the winter when slurry would have been spread. However, there was a lack of information about a number parameters that would be required to carry out a more exact calibration and provide a rigorous test of the modelling procedure. It was nevertheless concluded that through soil flow of colloid sorbed P by macropore flow represents a highly plausible mechanism by which P is transported to river systems in livestock farming catchments. This represents an alternative to surface runoff transport, a mechanism to which high P losses from livestock farming areas have often been attributed. The occurrence of high simulated levels of loss under wet conditions indicates environmental benefits from avoiding slurry spreading on wet soil or during rain, and from some forms of grazing management.     

Modelling Cryptosporidium oocysts transport in small ungauged agricultural catchments

Cryptosporidium is an environmentally robust pathogen that has caused severe waterborne disease outbreaks worldwide. The main source of zoonotic Cryptosporidium parvum oocysts in human drinking water is likely to be from farm animals via catchment pathways with water as the main transport vector. The vast majority of small agricultural catchments are ungauged therefore it is difficult to use a process model to predict and understand the mechanisms and activities that regulate the risk of surface water contamination from agricultural areas. For this study, two ungauged agricultural catchments in Ireland were used to model Cryptosporidium oocyst transport using SWAT2005 on a daily basis with reference data from adjacent catchment gauging stations. The results indicated that SWAT2005 could simulate stream flow with good agreement between prediction and observation on a monthly basis (R² from 0.94 to 0.83 and E (efficiency) from 0.92 to 0.66), but Cryptosporidium oocyst concentration results were less reliable (R² from 0.20 to 0.37, P < 0.05; with poor E −0.37 to −2.57). A sensitivity analysis using independent parameter perturbation indicated that temperature was the most important parameter regulating oocyst transport in the study catchments and that the timing of manure application relative to the occurrence of water runoff event was critical. The results also showed that grazing management had little influence on predicted oocyst transport while fields fertilized with manure were the key critical source areas for microbial contaminations in the study catchments. It was concluded that the approach presented could be used to assist with understanding the epidemiology of waterborne cryptosporidiosis outbreaks and to improve catchment management for the safety of the general public health.     

Catchment-specific element signatures in estuarine crocodiles (Crocodylus porosus) from the Alligator Rivers Region, northern Australia

The concentrations of Na, K, Ca, Mg, Ba, Sr, Fe, Al, Mn, Zn, Pb, Cu, Ni, Cr, Co, Se, U and Ti were determined in the osteoderms and/or flesh of estuarine crocodiles (Crocodylus porosus) captured in three adjacent catchments within the Alligator Rivers Region (ARR) of northern Australia. Results from multivariate analysis of variance showed that when all metals were considered simultaneously, catchment effects were significant (P < or = 0.05). Despite considerable within-catchment variability, linear discriminant analysis (LDA) showed that differences in elemental signatures in the osteoderms and/or flesh of C. porosus amongst the catchments were sufficient to classify individuals accurately to their catchment of occurrence. Using cross-validation, the accuracy of classifying a crocodile to its catchment of occurrence was 76% for osteoderms and 60% for flesh. These data suggest that osteoderms provide better predictive accuracy than flesh for discriminating crocodiles amongst catchments. There was no advantage in combining the osteoderm and flesh results to increase the accuracy of classification (i.e. 67%). Based on the discriminant function coefficients for the osteoderm data, Ca, Co, Mg and U were the most important elements for discriminating amongst the three catchments. For flesh data, Ca, K, Mg, Na, Ni and Pb were the most important metals for discriminating amongst the catchments. Reasons for differences in the elemental signatures of crocodiles between catchments are generally not interpretable, due to limited data on surface water and sediment chemistry of     

Increasing trends of total organic carbon concentrations in small forest lakes in Finland from 1987 to 2003

Trends in total organic carbon (TOC) concentrations over the period 1987-2003 were studied in 13 small forest lakes. Recovery from acidification (reduced SO(4) deposition) and long-term changes in runoff as potential drivers for the trends were examined. The results showed that TOC concentrations have increased throughout Finland. Ten of the 13 lakes showed a significant increasing TOC trend (p<0.05), and included both clear water and humic lakes. The largest annual increase in TOC occurred in lakes with the largest average concentrations. The magnitude of the TOC trends were not significantly related to the proportion of peat soils in the catchment but the catchment size was an important predictor. Decreasing SO(4) deposition and improved acid-base status in soil due to the recovery from acidification implied an increased mobilisation of organic acids and TOC. There was little evidence that the long-term increasing trend in TOC concentrations was related to long-term changes in runoff. However, large seasonal and inter-annual fluctuations in runoff did appear to affect TOC concentrations for a number of years.     

Sources of heavy metals and polycyclic aromatic hydrocarbons in urban stormwater runoff

Polycyclic aromatic hydrocarbons (PAHs) and heavy metals were measured in road debris collecting in urban areas and in the suspended sediment (SS) component of runoff from two stormwater catchments in Dunedin, New Zealand. Levels in the road debris ranged from 119-527 microg/g for lead, 50-464 microg/g for copper, 241-1 325 microg/g for zinc and 1.20-11.6 microg/g for sigma16PAH. The SS from the largely rural catchment (20% urban) had similar concentrations to the road debris, indicating that this urban material was the main source of the contaminants measured in the stormwater. Similar PAH fingerprint profiles and isomer ratios indicative of dominant pyrogenic (combustion) sources were also found in these two groups of materials. The SS from the 100% urban catchment contained 2- to 6-fold higher concentrations of metals and 10-fold greater levels of sigma16PAH. The higher levels of lead and copper were probably a result of industrial land uses in this catchment, while the additional zinc was linked to an abundance of zinc-galvanised roofing iron in the catchment's residential suburbs. The PAH profiles and isomer ratios were different for this urban catchment and suggested that a disused gasworks was contributing PAHs to the stormwater runoff.