Significance of urban and agricultural land use for biocide and pesticide dynamics in surface waters

Biocides and pesticides are designed to control the occurrence of unwanted organisms. From their point of application, these substances can be mobilized and transported to surface waters posing a threat to the aquatic environment. Historically, agricultural pesticides have received substantially more attention than biocidal compounds from urban use, despite being used in similar quantities.This study aims at improving our understanding of the influence of mixed urban and agricultural land use on the overall concentration dynamics of biocides and pesticides during rain events throughout the year. A comprehensive field study was conducted in a catchment within the Swiss plateau (25 km²). Four surface water sampling sites represented varying combinations of urban and agricultural sources. Additionally, the urban drainage system was studied by sampling the only wastewater treatment plant (WWTP) in the catchment, a combined sewer overflow (CSO), and a storm sewer (SS). High temporal resolution sampling was carried out during rain events from March to November 2007.The results, based on more than 600 samples analyzed for 23 substances, revealed distinct and complex concentration patterns for different compounds and sources. Five types of concentration patterns can be distinguished: a) compounds that showed elevated background concentrations throughout the year (e.g. diazinon >50 ng L⁻¹), indicating a constant household source; b) compounds that showed elevated concentrations driven by rain events throughout the year (e.g. diuron 100-300 ng L⁻¹), indicating a constant urban outdoor source such as facades; c) compounds with seasonal peak concentrations driven by rain events from urban and agricultural areas (e.g. mecoprop 1600 ng L⁻¹ and atrazine 2500 ng L⁻¹ respectively); d) compounds that showed unpredictably sharp peaks (e.g. atrazine 10,000 ng L⁻¹, diazinon 2500 ng L⁻¹), which were most probably due to improper handling or even disposal of products; and finally, e) compounds that were used in high amounts but were not detected in surface waters (e.g. isothiazolinones).It can be safely concluded that in catchments of mixed land use, the contributions of biocide and pesticide inputs into surface waters from urban areas are at least as important as those from agricultural areas.     

Stochastic modeling of total suspended solids (TSS) in urban areas during rain events

The load of total suspended solids (TSS) is one of the most important parameters for evaluating wet-weather pollution in urban sanitation systems. In fact, pollutants such as heavy metals, polycyclic aromatic hydrocarbons (PAHs), phosphorous and organic compounds are adsorbed onto these particles so that a high TSS load indicates the potential impact on the receiving waters. In this paper, a stochastic model is proposed to estimate the TSS load and its dynamics during rain events. Information on the various simulated processes was extracted from different studies of TSS in urban areas. The model thus predicts the probability of TSS loads arising from combined sewer overflows (CSOs) in combined sewer systems as well as from stormwater in separate sewer systems in addition to the amount of TSS retained in treatment devices in both sewer systems. The results of this TSS model illustrate the potential of the stochastic modeling approach for assessing environmental problems.     

Contributions of wastewater, runoff and sewer deposit erosion to wet weather pollutant loads in combined sewer systems

An observatory of urban pollutants was created in Paris for the purpose of assessing the dynamics of wastewater and wet weather flow (WW and WWF) pollutant loads within combined sewers. This observatory is composed of six urban catchments, covering land areas ranging in size from 42 ha to 2581 ha. For a wide array of parameters including total suspended solids (TSS), chemical and biochemical oxygen demand (COD and BOD₅), total organic carbon (TOC), total Kjeldahl nitrogen (TKN), heavy metals (Cu and Zn) and polycyclic aromatic hydrocarbons (PAHs), this article is intended to evaluate the contributions of wastewater, runoff and in-sewer processes to WWF pollutant loads through the use of an entry–exit mass balance approach. To achieve this objective, a total of 16 rain events were sampled on these sites between May 2003 and February 2006. This study has confirmed that at the considered catchment scale (i.e. from 42 ha to 2581 ha) the production and transfer processes associated with WWF pollutant loads do not vary with basin scale. Entry–exit chemical mass balances over all catchments and for a large number of rain events indicate that wastewater constitutes the main source of organic and nitrogenous pollution, while runoff is the predominant source of Zn. For Cu, PAHs and TSS, the calculation underscores the major role played by in-sewer processes, specifically by sediment erosion, as a source of WWF pollution. A significant loss of dissolved metals was also observed during their transfer within the sewer network, likely as a consequence of the adsorption of dissolved metals on TSS and/or on sewer deposits. Moreover, the nature of eroded particles was examined and compared to the various sewer deposits. This comparison has highlighted that such particles exhibit similar organic and PAH contents to those measured in the organic layer, thus suggesting that the deposit eroded during a wet weather period is organic and of a nature comparable to the organic layer. Despite the extent of initial field investigations, no organic deposit was observed to be present on sewer lines within the catchments, which implies that this organic deposit is probably present in another form or to be found elsewhere in the main trunks.     

Occurrence of pesticides in rain and air in urban and agricultural areas of Mississippi, April-September 1995

In April 1995, the US Geological Survey began a study to determine the occurrence and temporal distribution of 49 pesticides and pesticide metabolites in air and rain samples from an urban and an agricultural sampling site in Mississippi. The study was a joint effort between the National Water-Quality Assessment and the Toxic Substances Programs and was part of a larger study examining the occurrence and temporal distribution of pesticides in air and rain in the Mississippi River basin. Concurrent high-volume air and wet-only deposition samples were collected weekly. The air samplers consisted of a glass-fiber filter to collect particles and tandem polyurethane foam plugs to collect gas-phase pesticides. Every rain and air sample collected from the urban and agricultural sites had detectable levels of multiple pesticides. The magnitude of the total concentration was 5-10 times higher at the agricultural site as compared to the urban site. The pesticide with the highest concentration in rain at both sites was methyl parathion. The pesticide with the highest concentration in the air samples from the agricultural site was also methyl parathion, but from the urban site the highest concentration was diazinon followed closely by chlorpyrifos. More than two decades since p,p'-DDT was banned from use in the United States, p,p'-DDE, a metabolite of p,p'-DDT, was detected in every air sample collected from the agricultural site and in more than half of the air samples from the urban site.     

Source characterisation and loads of metals and pesticides in urban wet weather discharges

Contaminants in urban wet weather discharges originate from a number of sources such as materials from wet and dry atmospheric deposition, wastewaters, urban surface erosion, traffic-related activities, in-sewer deposits, etc. In the current study, four contributions (rainwater, dry atmospheric deposition, dry weather discharge and catchment surface + possible erosion of in-sewer deposits) to the total concentrations of priority substances have been assessed at the outlet of two urban catchments (one residential catchment with a combined system and one industrial area with a separate stormwater system) for 12 storm events (six for each catchment). Mass balances were calculated for seven metals and four pesticides, as well as for total suspended solids and chemical oxygen demand. The respective contributions of dry and wet atmospheric deposition, wastewater and catchment surface differ for each pollutant type, corresponding to different land use, activities, environments and sewer systems. For most of the pollutants, the catchment surface appears to be the main contribution, with significant storm event variability, excepted for atrazine in one catchment.     

Modelling biocide leaching from facades

Biocides leach from facades during rain events and subsequently enter the aquatic environment with storm water. Little is known about the losses of an entire settlement, since most studies referred to wash-off experiments conducted under laboratory conditions. Their results show a fast decrease of concentrations in the beginning, which subsequently slows down. The aim of this study is to develop a simple model to understand the mechanisms leading to these losses as well as to simulate losses under various rainfall and application conditions.We developed a four-box model based on the knowledge gained from fits of an exponential function to an existing experimental data set of a wash-off experiment. The model consists of two mobile stocks from which biocides are washed off during a rain event. These mobile stocks are supplied with biocides from storage stocks by diffusion-type processes. The model accurately reproduced the measured data of wash-off during single cycles as well as peak wash-offs over all cycles.Our model results for diuron losses showed that a large proportion (∼70%) of the applied biocides are still in the stocks even after a rain volume corresponding to several years (1100 mm y⁻¹, Swiss Plateau). Applications to realistic outdoor conditions showed that losses can not be neglected for urban environments and that knowledge about the amount of rainfall turned into runoff and the decay constants of the biocides in the facades are crucial. The model increased our understanding of the processes leading to the observed dynamic in laboratory experiments and was used to simulate losses for various rainfall and application conditions.     

Contribution of different sources to the pollution of wet weather flows in combined sewers

Experiments performed on "Marais" catchment, in central Paris, aimed to follow up the quality of wet weather flows from the entry to the exit of a combined sewer network. SS, VSS, COD, BOD5, Cd, Cu, Pb, Zn concentrations were measured for an important number of rain events in roof, yard, street runoff, as well as in dry and wet weather flows at the catchment outlet. Mass entry-exit totals, at the scale of the catchment, were calculated over 31 rain events in order to evaluate the contribution of different types of runoff, of sanitary sewage and of sewer sediments to the total wet weather pollutant loads at the catchment outlet. The erosion of in-sewer pollutant stocks was found to be the main source of particles and of organic matter in wet weather flows, whereas heavy metal loads mainly originated from roof runoff, due to the corrosion of metallic roofs. Particles eroded inside the sewer during rain events were found to be quite different from the particles constituting the main part of sewer sediments: they are organic and biodegradable, with rather important settling velocities and seem to accumulate during dry weather periods. A change of the chemical form of heavy metals was noticed during the transport in the sewer and it is suspected that a fraction of the dissolved metals from the runoff is adsorbed on sewer sediments.     

Stream cation concentrations and losses from drainage basins with contrasting land uses in Southern Ontario

The concentration and loss of major cations from 22 watersheds near Toronto, Ontario, was measured over a 27-month period. Calcium and potassium concentrations exhibited a positive relationship with crop area and a negative correlation with abandoned farm land + forest and areas of sand + sandy loam soil. The influence of soil properties and farming activities on streám cation levels could not be separated because of multicollinearity between land use and soils. An absence of correlation between crop area and annual losses of calcium and potassium can be attributed to lower annual stream discharges in agricultural watersheds in comparison to watersheds containing extensive areas of forest and abandoned farm land. Stream concentrations and losses of potassium and sodium were positively correlated with urban land use. Detailed water sampling in the vicinity of urban centres confirmed that these areas are important contributors of sodium, and to a lesser extent, of potassium to streams. Magnesium concentration was influenced mainly by differences in watershed hydrology and no correlation was evident with urban or agricultural land use.     

Assessment of the Fate of Selected Adsorptive Pesticides at ADAS Rosemaund

Data are presented on four pesticides applied to agricultural land at the Agricultural Development Advisory Service, Rosemaund, in the west of England. The farm covers a well-defined and isolated water basin of cracking heavy clay loam soils drained by a single stream. Levels of the relatively particle-bound pesticides trifluralin, deltamethrin, chlorpyrifos and fenpropimorph were measured in drainage water and field soils following application. Observed concentrations in water were generally below 1 μg/l with occasional peak levels exceeding 10 μg/l during storm rainfall events. Unexpectedly high peak levels of deltamethrin of around 2 μg/l highlighted significant bypass flow mechanisms from the surface soils during the autumn. Additional bioassay experiments showed that levels of chlorpyrifos, lethal to Gammarus pulex , reached the stream during spring 1993. The Rosemaund farm has been the site of a continuing investigation into the movement of agricultural pesticides to surface waters since 1987, and this report represents the final work conducted in the autumn of 1992 and spring 1993.     

Pesticide Transport to Surface Waters within an Agricultural Catchment

This paper presents data on the distribution of seven pesticides in an agricultural catchment which is located within the Agricultural Development and Advisory Service farm at Rosemaund, 11 km north-east of Hereford, UK. Data for aldicarb, atrazine, carbofuran, dimethoate, MCPA and isoproturon, are available for both the soil and surface waters (drain and stream water), with simazine data available only for the stream. Measurements were taken before and after pesticide application, which was made following normal agricultural practice. Soil residue data showed the degradation rates of the pesticides to be within the range of literature values. Pesticide levels in the stream and drains during runoff events following rainfall ranged from below detection limits (typically 0.02-0.1 μg/1), to 264 μg/1 (for carbofuran). Over 90% of the events had detectable maximum concentrations. The percentage of pesticide applied, which was removed during individual rainfall events, was calculated. The maximum value estimated was 1.1%, again for carbofuran. Most of the events gave values several orders of magnitude below this value.
The data have been used to try to validate a range of models which could be used for screening new pesticides or for informing decisions on the use of existing pesticides. The results of the validations are summarized.     

A case study of urban water balancing in the partly sewered city of Nablus-East (Palestine) to study wastewater pollution loads and groundwater pollution

Untreated sewage can contribute a significant proportion of urban groundwater recharge, via on-site sanitation facilities and sewer exfiltration. In the West Bank of the Palestinian Territories 94% of sewage is discharged untreated to the ground or surface waters. This has contributed to increasing nitrate concentrations in groundwater, which is the critical water source. In this case study of a drainage catchment from the city of Nablus, a water balance indicates that sewage as a source of groundwater recharge is as much as 50% of total recharge from precipitation, and nitrogen pollutant loads by area are up to 60% as much as those from agriculture. Results suggest that 22% of total wastewater flow directly infiltrates the ground via cesspits and sewer exfiltration.     

Wastewater quality and pollutant loads in combined sewers during dry weather periods

An observatory of urban pollutants was created in Paris in order to assess, at the urban catchment scale, the quality of sanitary sewage and pollutant loads during dry weather periods in the Paris combined sewer. Investigations were carried out for six urban catchments (varying from 42 to 2580 ha) focusing on a wide range of parameters, including: suspended solids (SS), chemical and biochemical oxygen demand (COD and BOD₅), total organic carbon (TOC), total Kjeldahl nitrogen (TKN), heavy metals (Cd, Cu, Pb, Zn), and aliphatic and polycyclic aromatic hydrocarbons (AHs and PAHs). Despite the marginal intra-site variability of some pollutants, which serves to reflect the impact of point sources, this work attests to the spatial homogeneity, at the physical scales considered, of wastewater quality and pollutant loads within the Paris combined sewer network. These results imply that similar production and transfer processes are occurring within sewers during dry weather periods and strongly suggest that data obtained on one specific catchment could be extrapolated to smaller or larger catchments that display quite similar land use and sewer characteristics.     

Contribution by urban and agricultural pesticide uses to water contamination at the scale of the Marne watershed

This study establishes an annual watershed (12,762 km(2)) budget of pesticide contamination in the Marne River based on detailed enquiries from farmers' organizations, public services and residents and pesticide usage. Results showed that urban uses were considerably lower (47 tons/yr) than agricultural ones (4300 tons/yr). However, the proportion of the amounts used transferred to surface water, differs considerably between urban and agricultural environments. Transfer from urban uses was estimated from runoff experiments with different surfaces, including concrete, tarmac, sand and gravel, and grass. Transfer coefficients from agricultural uses were derived from the calibrated value previously obtained from a detailed budget established for atrazine, taking into account the specific adsorption capacity (Koc) and half-life time of each substance used. The calculated annual budget shows a similar contribution by urban pesticides in the Marne River due to runoff over impervious surfaces as compared to agricultural pesticides used on cultivated soils (about 11 tons/yr in both cases). These estimates are consistent with data available from analytical surveys concerning pesticide occurrence in the rivers of the Paris region.     

Contribution of combined sewer overflows to trace contaminant loads in urban streams

The present study examines the contribution of combined sewer overflows (CSO) to loads and concentrations of trace contaminants in receiving surface water. A simple method to assess the ratio of CSO to wastewater treatment plant (WWTP) effluents was applied to the urban River Spree in Berlin, Germany. The assessment indicated that annual loads are dominated by CSO for substances with removal in WWTP above ∼95%. Moreover, it showed that substances with high removal in WWTP can lead to concentration peaks in the river during CSO events. The calculated results could be verified based on eight years of monitoring data from the River Spree, collected between 2000 and 2007. Substances that are well removed in WWTP such as NTA (nitrilotriacetic acid) were found to occur in significantly increased concentration during CSO, while the concentration of substances that are poorly removable in WWTP such as EDTA (ethylenediaminetetraacetic acid) decreased in CSO-influenced samples due to dilution effects. The overall results indicate the potential importance of the CSO pathway of well-removable sewage-based trace contaminants to rivers. In particular, high concentrations during CSO events may be relevant for aquatic organisms. Given the results, it is suggested to include well-removable, sewage-based trace contaminants, a substance group often neglected in the past, in future studies on urban rivers in case of combined sewer systems. The presented methodology is suggested for a first assessment, since it is based solely on urban drainage data, which is available in most cities.     

雨污分流改造保留合流管为雨水管的工程实例

在将城市排水合流管改造为雨、污分流管道的过程中，如条件允许可将合流管局部或整体保留用做雨水管，再另外新建污水管道。结合苏州市中心城区完善污水管网工程，介绍了在该市吴县新村内的应用实例。实践表明，保留的合流管能有效地排放正常年份的降雨，甚至是台风暴雨时产生的地面径流。该措施不仅能节约工程投资、缩短工期，还能减少因地面开挖对居民生活造成的不利影响。     

Probabilistic modelling of overflow, surcharge and flooding in urban drainage using the first-order reliability method and parameterization of local rain series

Failure of urban drainage systems may occur due to surcharge or flooding at specific manholes in the system, or due to overflows from combined sewer systems to receiving waters. To quantify the probability or return period of failure, standard approaches make use of the simulation of design storms or long historical rainfall series in a hydrodynamic model of the urban drainage system. In this paper, an alternative probabilistic method is investigated: the first-order reliability method (FORM). To apply this method, a long rainfall time series was divided in rainstorms (rain events), and each rainstorm conceptualized to a synthetic rainfall hyetograph by a Gaussian shape with the parameters rainstorm depth, duration and peak intensity. Probability distributions were calibrated for these three parameters and used on the basis of the failure probability estimation, together with a hydrodynamic simulation model to determine the failure conditions for each set of parameters. The method takes into account the uncertainties involved in the rainstorm parameterization. Comparison is made between the failure probability results of the FORM method, the standard method using long-term simulations and alternative methods based on random sampling (Monte Carlo direct sampling and importance sampling). It is concluded that without crucial influence on the modelling accuracy, the FORM is very applicable as an alternative to traditional long-term simulations of urban drainage systems.     

Diffuse and point pollution impacts on the pathogen indicator organism level in the Geum River, Korea

The pathogens originating from diffuse pollution have raised much concern recently. In many countries, pathogen levels are monitored in surface water by measuring the pathogen indicator organism level, which indicates the concentration of pathogen associated microorganisms to determine contamination. Among indicator organisms, total coliform, fecal coliform, and Escherichia coli were selected for study, and their concentration as well as their flow rate were monitored at monitoring stations from October, 2001 to April, 2003. Monitoring stations include six sampling stations in the Geum River, two small watersheds used for forestry and agricultural land, one large wastewater treatment plant, one separate sewer overflow site, and one separate sewer overflow site in the Geum River basin. The coliform concentration of the combined sewer overflow was the highest, followed by the runoff from agricultural land use, the separate sewer overflow, and the runoff from forestry land use. The Pearson correlation coefficient for flow rate against total coliform concentration was 0.71 and was significant at 0.01 level, while the Pearson coefficient for other water quality constituents showed weak correlation (-0.36 to +0.37) against flow rate. Coliform concentration showed higher correlation against suspended solid concentration or flow rate during storm flow condition than during low flow condition. Two different relationship lines could explain the relationships between the flow rate and coliform loadings. Load duration curve technique was presented to assess the relative contributions of diffuse and point source pollution to the pathogen level at monitoring sites in the Geum River.     

Long-term sodium and chloride surface water exports from the Dallas/Fort Worth region

Sodium and chloride in surface water are typically related to urbanization and population density and can have a significant impact on drinking water sources and the subsequent salinity of aquatic ecosystems. While the majority of research has focused on the impact of deicing salts on urban surface waters in colder climates, the effect of urbanization on sodium and chloride concentrations has been found to occur in warmer climates. This study investigated long-term exports of sodium and chloride from watersheds with increasing urbanization in the humid subtropical Dallas-Fort Worth region. We compared exports to characteristics of urbanization: urban land cover, impervious surface area, and calculated contributions from wastewater discharges. Long-term data (1980-2008) were obtained from five USGS gages located in and around the cities. Exports were calculated by regression analysis between concentrations and discharge and normalized for time and the watershed area. Grab samples were collected from June 2009 to May 2010 and sodium and chloride concentrations quantified. Our results show a strong positive relationship between the mean annual sodium and chloride exports from each watershed and the percent urban land cover and impervious surface area. Long-term increases in sodium and chloride fluxes were found for the three watersheds with the highest percentage of urban land cover. The single largest contributor was wastewater effluent that was estimated to contribute approximately half of the total loads in the three urbanized watersheds. Atmospheric deposition and deicing salts accounted for small amounts of the total export for urbanized watersheds. The source of the remaining salt load is still unknown and may be a combination of non-point sources. Estimates of urban salt exports were similar to estimates from northern watersheds affected by deicing salts.     

Soil erosion as a result of the man activity-geological environment relationship an example of quantitative evaluation in the mugello valley (Tuscany,Italy)

The spreading mechanization of the agricultural activities has determined, in the last decades, an enlargement of the fields generally obtained from natural landforms rearrangement without the employment of the necessary support practices. It has brought about a break in the weak equilibrium between the old agricultural practice and the geological environment, increasing on sloping fields morphogenetic processes and especially soil erosion. Therefore the evaluation of soil losses amount assumes a basic role in the agricultural planning. After a synthetic and critical review of the more diffuse methodologies for the evaluation of the erosion risks, a new field rain simulator is briefly described, which rapidly allows to obtain reliable practical answers. The study area was subdivided in homogeneous units for climatic, lithologic, pedologic, morphometric and land use characteristics (land units map). The employed methodology including the use of rain simulator, establishes, for each unit, the analysis of the relation between antropic activities (agricultural practices) and soil erosion, in function of the most important factors acting in the erosive process (rain erosivity, soil erodibility, slope length and gradient, crops and support practices). In this report the results related to the “Mugello Lacustrine Clay” unit are reported; this unit is a part of the sample area under study (Mugello Valley, Tuscany, Italy), and it is representative of a large extension in the ancient interappenninic lacustrine basins.     

On hydraulic and pollution effects of converting combined sewer catchments to separate sewer catchments

The overall objective of this paper is to contribute to the standing debate concerning the advantages of separate sewer systems compared to traditional combined sewer systems. By a case study this investigation reveals that transformation of part of a town from being serviced with combined sewer systems to become serviced with separate sewer systems decreases the volumes of storm water and pollutants diverted to the waste water treatment plant and discharged as combined sewer overflow. This happens at the expense of an increase in volumes of storm water and pollutant loads diverted to local receiving waters when detention ponds are not built-in the new separate sewer systems. It is concluded that consequences can be fatal for receiving waters, if no retention of pollutants is integrated into the system.