Spatial and temporal distribution of pesticide residues in surface waters in northeastern Greece

A monitoring study of 147 compounds in surface river waters from northeastern Greece near Greek/Bulgarian/Turkish borders was carried out during 1999-2007. Based on agricultural use eight sampling points along the rivers Ardas, Evros and Erythropotamos were set up, covering the distance from the Greek/Bulgarian borders down to the river's discharge (river's delta) in the Greek territory. In total, 88 sampling events were carried out from 1999 to 2007. Pesticides were extracted by solid-phase extraction (SPE) and analyzed by gas chromatography-mass spectrometry (GC-EI-MS) using a multiresidue in-house analytical method including pesticides belonging to different chemical classes. Aquatic risk concerning the detected pesticides was assessed on the basis of the risk quotient (RQ = PEC/PNEC). From the 28 compounds (pesticides, metabolites and caffeine) that were detected in surface waters of northeastern Greece the soil applied pesticides were the most frequently detected. High pesticide concentrations were detected within 2 months of their application. Extreme pesticide concentrations were detected in the beginning of the irrigation season or just after high rainfall events. Generally, low levels of pesticide residues were found in the first sampling point (Greek/Bulgarian borders) of all rivers, however o′,p′ DDT, o′,p′ DDE and γ-HCH were mainly detected in this sampling point regarded as cross-boundary contamination. The most commonly encountered compounds in the river waters were atrazine, DEA, alachlor, trifluralin, prometryne, molinate, carbofuran, carbaryl and diazinon. Increased loading (primary as well as secondary peaks) seemed to be a consequence of application (timing, rate, frequency) and intense rainfall during the application period. Aquatic risk assessment revealed that from the 28 compounds that were constantly detected 12 showed non-acceptable risk when median concentrations were used as PEC and 18 when extreme concentrations were used as PEC values.     

Organic compounds in typical surface waters of the northern part of Western Siberia

The article presents the results of hydrochemical research conducted at the end of August 2014 and in spring 2013 in the northern part of Western Siberia. The research concerns unfiltered waters of small streams, medium-sized rivers, the Ob’ River and two large thermokarst lakes. A special mobile laboratory enabled the research team to conduct many on-site analyses several hours after the collection of samples. The results have been assessed in terms of their significance for the general quality evaluation of the examined waters and the nature of organic substances contained in the waters. Additionally, the paper discusses results of chemical and physical tests to evaluate the amount of organic substances. General features concerning the evaluation of organic compounds among different type of surface waters have been suggested on the basis of the studies.     

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.     

Runoff-related agricultural impact in relation to macroinvertebrate communities of the Lourens River, South Africa

A field study at the Lourens River, South Africa, was undertaken during the pesticide application period between November 2001 and January 2002 in order to investigate the potential relation of agricultural pollution to the aquatic macroinvertebrate fauna. The upper regions of the Lourens River were free of contamination (LR1), whereas subsequent stretches flowing through a 400-ha orchard area (LR2) received transient insecticide peaks. Continuously operating suspended-particle samplers as well as flood samplers operating during runoff events were used to measure pesticide contamination. In addition, various physicochemical and morphological parameters were examined. A survey of the macroinvertebrate communities associated with the rocky substrates was carried out every three weeks. Community indices were calculated using the South African Scoring System (SASS 5) for bioassessment of water quality in rivers. The two sites differed in pesticide pollution as well as in average turbidity levels (LR1 5.5 mg/L; LR2 64.3 mg/L), but were similar in bottom substrate composition and most other abiotic factors. At the downstream site (LR2), pesticide values of 0.05 microg/L azinphos-methyl in water as well as 49 microg/kg azinphos-methyl, 94 microg/kg chlorpyrifos and 122 microg/kg total endosulfan in suspended particles were found during runoff conditions. The macroinvertebrate communities of the two sampling sites were similar in terms of number of total individuals, but differed significantly (ANOVA) in average number of taxa (LR1 11.7, LR2 8.9). Seven out of 17 investigated taxa occurred in significantly reduced numbers or were even absent at the downstream site LR2. The community characteristics determined by SASS 5 showed a significantly less sensitive community structure at the downstream site (TS 41; ASPT 4.6), indicating continuously lower water quality compared to site LR1 (TS 80; ASPT 6.9). It is concluded that the Lourens River macroinvertebrate communities are affected by agricultural pollution, with pesticides and increased turbidity as the most important stressors.     

Removal of pesticide mixtures in a stormwater wetland collecting runoff from a vineyard catchment

Wetlands can collect contaminated runoff from agricultural catchments and retain dissolved and particle-laden pesticides. However, knowledge about the capacity and functioning of wetland systems with respect to the removal of pesticides is very limited. Here we show that stormwater wetlands can efficiently remove pesticides in runoff from vineyard catchments during the period of pesticide application, although flow and hydrochemical conditions of the wetland largely vary over time. During the entire agricultural season, the inflowing load of nine fungicides, six herbicides, one insecticide and four degradation products was 8.039 g whereas the outflowing load was 2.181 g. Removal rates of dissolved loads by the wetland ranged from 39% (simazine) to 100% (cymoxanil, gluphosinate, kresoxim methyl and terbuthylazine). Dimethomorph, diuron, glyphosate, metalaxyl and tetraconazole were more efficiently removed in spring than in summer. More than 88% of the input mass of suspended solids was retained, underscoring the capability of the wetland to trap pesticide-laden particles via sedimentation. Only the insecticide flufenoxuron was frequently detected in the wetland sediments. Our results demonstrate that stormwater wetlands can efficiently remove pesticide mixtures in agricultural runoff during critical periods of pesticide application, although fluctuations in the runoff regime and hydrochemical characteristics can affect the removal rates of individual pesticides.     

Priority pollutants in surface waters and settleable particles within a densely urbanised area: Case study of Paris (France)

Implementation of the European Water Framework Directive 2000/60/EC (WFD) requires Member States to expand their collective knowledge of priority pollutants (PPs) within receiving waters. To achieve this objective, information on the occurrence of PPs in surface waters and, more specifically, within densely urbanised areas needs to be collected. This study has therefore been designed to provide information on both PP occurrence and concentration build-up along a heavily urbanised transect of the Seine River in the Paris region (France). A large range of PPs were observed in settleable particles and, to a lesser extent, in the waters surveyed. In surface waters, a total of 18 PPs, including 15 priority hazardous substances?, were indeed detected, yet concentrations rarely exceeded the limit of quantification. In fact, only diuron?, DEHP?, fluoranthene and para-tert-octylphenol? are observed on a frequent basis, with concentrations ranging from < 0.01 to 1.0 µg l^− 1. As regards the Environmental Quality Standards (EQS), 10 substances or groups of substances were found in surface waters to exhibit concentrations above the annual average value, while only the benzo(a)pyrene? concentration exceed the maximum allowable level. As for the Canadian Sediment Quality Guidelines, settleable particles collected in the Seine River appear to be heavily contaminated since most samples contain PP levels above the guideline values (18 PPs) and, in many cases, above the probable effect levels (15 PPs), which underscores that the levels of metals, PAHs and PCBs in settleable particles constitute a potential risk to freshwater organisms.     

Pesticides in Portuguese surface and ground waters

Pesticides used in Portuguese agricultural areas have been found in surface and ground waters. In the surface water collected in three river basins from 1983 to 1999, insecticides and herbicides were detected from the monitored pesticides, particularly atrazine, chlorfenvinphos (Z+E), alpha- and beta-endosulfan, lindane, molinate and simazine, reaching the maximum values, respectively, of 0.63, 31.6, 0.18 microg/L (alpha-endosulfan), 0.18 microg/L (beta-endosulfan), 0.24, 48 and 0.3 microg/L. In the ground water collected from the wells of seven agricultural areas from 1991 to 1998, several monitored herbicides were detected: alachlor, atrazine, metolachlor, metribuzine and simazine, reaching the maximum concentration values of 13, 30, 56, 1.4 and 0.4 microg/L, respectively. The herbicides more frequently detected were atrazine (64%), simazine (45%) and alachlor (25%). Other than these, the monitored pesticides can be present in Portuguese surface and ground waters. Therefore, to improve the analytical conditions, the use of multiresidue methods and automated techniques are desirable in future work.     

Phototransformation of selected human-used macrolides in surface water: Kinetics, model predictions and degradation pathways

The phototransformation of clarithromycin and roxithromycin, two human-used macrolide (MLs) antibiotics was investigated in surface waters. Photolysis kinetic data suggest that degradation in water would occur via the direct photolysis of the Fe(III)-MLs complexes. Hydroxyl radicals, singlet oxygen and other photooxidants generated from nitrate ions and from excited chromophores present in humic acids appeared to have only a very limited impact on the overall degradation of MLs under the adopted UV-vis irradiation conditions. A photolysis model applied to the Fe(III)-clarithromycin complex in river water showed that a half-life of 40 days was predicted under clear-sky irradiation in November, 26 days in February, and 10 in May. Direct photolysis could have a limited impact on the environmental concentrations of MLs in rivers, due to a too short water residence time but might be important in shallow lakes and lagoons. Photoinduced degradation of MLs mainly implied changes in the structure of the aglycone, probably leading to their detoxification because the pseudoerythromycin derivatives have very little antimicrobial activity.     

Methyl bromide in surface drinking waters: Gas-chromatographic determination by the headspace technique

A sensitive method for the gas-chromatographic determination of methy bromide in surface drinking waters is reported. The analytical principle is based on the conversion of methyl bromide into methyl iodide by reaction with sodium iodide. Reaction parameters (amount of sodium iodide added, temperature, reaction time and salinity) are reported to provide a simple, precise and sensitive analytical method with a CH₃Br detection threshold of approx. 5 × 10⁻³μgl⁻¹.     

Mercury distribution in waters and fishes of the upper Madeira rivers and mercury exposure in riparian Amazonian populations

In this paper, the results of mercury concentrations in two abiotic compartments (river water and suspended particles) and two biotic compartments (fish and human hair) from the upper Madeira rivers of the Bolivian Amazon basin are presented. Because of the local hydrological regimes and a high deposition rate in the plain, due to the presence of a subsidence zone at the bottom of the Andean piedmont, in the dry season, the highest mercury concentrations and fluxes were not found in rivers where mining activities took place (2.25–6.99 ng l⁻¹; and 1.07–8.67 mg Hg d⁻¹ km⁻²), but at the outlet of the Andean basins exploited for their alluvial gold (7.22–8.22 ng l⁻¹; and 9.47–9.52 mg Hg d⁻¹ km⁻²). The total mercury concentrations measured in surface waters of the upper Beni basin varied during the dry season, from 2.24 to 2.57 ng l⁻¹ in the glacial waters of the Zongo river, to 7.00 ng l⁻¹ in the Madeira River at Porto Velho and 9.49–10.86 ng l⁻¹ at its confluence with the Amazon. The results obtained from fish indicate, on one hand, that 86% of the piscivorous fishes collected in the Beni river were contaminated, and, on the other hand, their high mercury concentrations could exceed by almost four times the WHO (1976) safety limit. In the Beni River, the mercury concentrations found in omnivorous and mud-feeding fish ranged from 0.02 to 0.19 μg g⁻¹ (wet wt.), and in piscivorous fish, from 0.33 to 2.30 μg Hg g⁻¹ (wet wt.). The mercury accumulated by carnivorous fishes was mainly present in its organic form; methylmercury represented 73–98% of the total mercury analysed. Eighty persons were studied in the entire Bolivian Amazonian basin. Unlike the gold miners, who are more affected by tropical diseases, such as malaria and yellow fever, the indigenous people living on the banks of the Beni river, present elevated levels of mercury (9.81 μg g⁻¹ on average). We observed an increase in contamination in young children still being breast-fed, confirming that hair mercury concentration in babies was significantly affected by maternal mercury contamination during pregnancy. These results show that the major health impacts caused by mercury affect people who are not working directly in gold mining activities but who have a regular fish diet.     

Organochlorinated pesticide multiresidues in surface sediments from Beijing Guanting reservoir

For the analysis of organochlorine pesticides (OCPs) in sediments and water, a multiresidue analysis method based on gas chromatography with electron capture detection (GC/ECD) was developed. Solid-phase extraction (SPE) using Oasis HLB cartridges was also applied in sample extraction. Mean recoveries were satisfactory with 72-103% and 71-103% for water and sediment, respectively. Twenty-one OCPs were analyzed in water and surface sediment samples from Beijing Guanting reservoir. Total concentrations of 21 OCPs were 16.7-791 ng/l (mean 234 ng/l), 275-1,600 ng/l (mean 644 ng/l), 5250-33,400 ng/kg (mean 13,000 ng/kg) in surface water, pore water and sediment (dry weight), respectively. P, p'-DDE, delta-HCH, aldrin, gamma-HCH and beta-HCH are the most abundant compounds in water while p, p'-DDE, o, p'-DDT, beta-HCH, delta-HCH, p, p'-DDT and aldrin accounted for about 85% of total 21 OCPs in sediment in Beijing Guanting reservoir. Concentrations of OCPs were high both in water and sediment samples in Beijing Guanting reservoir for municipal water supply. The data provides information on the levels and sources of OCPs in Guanting reservoir. The study indicated that measures should be taken to decrease OCPs residues in order to improve the quality of municipal water supply in Beijing.     

Underground sources of nutrient contamination to surface waters in Bangkok, Thailand

Radon-222 is very concentrated in groundwater relative to surface waters and thus serves as an effective groundwater discharge tracer. We observed spikes in radon data from an earlier (2004) survey of the Chao Phraya River that appeared to correspond to locations where major canals (“klongs”) enter the river. We returned in 2006 and conducted more detailed surveys along some of the main klongs on the western (Thonburi) side of the Chao Phraya to evaluate this possibility.Our results show that both radon and conductivity are enriched in some areas of the klongs with 3 apparent “end-members,” two of which are likely related to groundwater seepage. Furthermore, nutrient analyses conducted during a time-series experiment at a site of suspected high discharge (Wat Intharam, Klong Bangkok Yai) showed that dissolved inorganic nitrogen (DIN) and phosphate correlated significantly to the groundwater tracer, radon. Rough estimates of the nutrient fluxes in this area are orders of magnitude higher than those measured in coastal settings and may represent a significant fraction of the riverine flux. It thus appears very likely that seepage of shallow groundwater is an important pathway for nutrient contamination of the klongs, and thus to the river, and ultimately to the Gulf of Thailand.     

Limestone neutralization of acid waters in the presence of surface precipitates

Acid waste waters are usually treated by means of lime in order to meet pH requirements for discharge. Considerable saving may be achieved using limestone in neutralization processes.The feasibility of limestone neutralization processes also in those cases where precipitates form both on the reactive surface and in the liquid bulk as pH rises has been evaluated.Experiments were carried out with a well mixed tank reactor contacting limestone with acid solutions containing iron (III) sulphate and sulphuric acid. Analyses for calcium and iron (III) concentrations as well as for CO₂ desorption rate for their changes with time and continuous recording of pH were carried out during each run.The results show that neutrality can be achieved within a few minutes providing the operation conditions ensure a continuous removal of precipitates from the reacting surface.A critical comparison with previous results concerning a similar system containing AlCl₃ and HCl emphasizes the phenomenological differences between the two systems.The kinetic model for limestone dissolution in acid solutions previously developed has been successfully applied to the system studied.     

The occurrence of selected pharmaceuticals in wastewater effluent and surface waters of the lower Tyne catchment

This paper presents the results of a survey of the wastewater effluent and surface waters of the lower river Tyne, UK. Samples were analysed by reversed-phase high-performance liquid chromatography-electrospray tandem mass spectrometry following solid phase extraction, for the presence of 13 pharmaceuticals selected from the priority lists of the UK Environment Agency and the Oslo and Paris Commission (OSPAR). The pharmaceutical compounds measured were acetyl-sulfamethoxazole, clofibric acid, clotrimazole, dextropropoxyphene, diclofenac, erythromycin, ibuprofen, mefenamic acid, paracetamol, propranolol, sulfamethoxazole, tamoxifen and trimethoprim. Of the wastewater treatment works (WTW) samples (n=9) analysed, all compounds except sulfamethoxazole and acetyl-sulfamethoxazole were detected at concentrations ranging from 11 to 69,570 ng l(-1) (in raw effluent). In the surface water samples (n=18), clotrimazole, dextropropoxyphene, erythromycin, ibuprofen, propranolol, tamoxifen and trimethoprim were detected at concentrations ranging from 4 to 2370 ng l(-1). Results of this study show that various pharmaceutical compounds are effectively reduced during their passage through a tertiary wastewater treatment works, whilst others are sufficiently persistent to occur in estuarine systems.     

Analyses and assessment of the spatial and temporal distribution of nitrogen compounds in surface waters

The temporal concentration variations and spatial distribution of nitrogen compounds (nitrate, nitrite, ammonium) in the natural surface waters of Stara Zagora Region, Bulgaria, over a period of 1 year were assessed in the present study. Nitrate‐nitrogen concentrations in all surface water samples, except for the December value – 21.8 mg/L in Zetyovo Reservoir, were within the permissible national quality standards. NO₂ ^–‐N could be classified as a priority pollutant of Chirpan and Zetyovo Reservoirs waters. The greatest extent of NH ₄ ⁺‐N pollution was registered in Chirpan Reservoir surface waters. The correlation study revealed appreciable mutual relationship only between NH₄ ⁺‐N and NO ₂ ^–‐N in the surface waters. The hierarchical cluster analysis (HCA) exhibited divergent apportionment of nitrogen compounds in the surface water bodies.     

Perfluorinated compounds in surface waters and WWTPs in Shenyang, China: mass flows and source analysis

Concentrations of 10 perfluorinated chemicals (PFCs) were investigated in the Hun River (HR), four canals, ten lakes, and influents and effluents from four main municipal wastewater treatment plants (WWTPs) in Shenyang, China. Mass flows of four main PFCs were calculated to elucidate the contribution from different sections of the HR. Overall, perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA) were the major PFCs in the HR, with ranges of 2.68-9.13 ng/L, and 2.12-11.3 ng/L, respectively, while perfluorooctane sulfonate (PFOS) was detected at lower levels, ranging from 0.40 to 3.32 ng/L. The PFC concentrations in the HR increased after the river passes through two cities (Shenyang and Fushun), indicating cities are an important contributor for PFCs. Mass flow analysis in the HR revealed that PFC mass flows from Fushun are 1.65-5.50 kg/year for C6-C8 perfluorinated acids (PFCAs) and 1.29 kg/year for PFOS, while Shenyang contributed 2.83-5.18 kg C6-C8 PFCAs/year, and 3.65 kg PFOS/year. The concentrations of PFCs in four urban canals were higher than those in the HR, with the maximum total PFCs of 240 ng/L. PFOA and PFOS showed different trends along these canals, suggesting different sources for the two PFCs. Total PFCs in ten lakes from Shenyang were at low levels, with the greatest concentration (56.2 ng/L) detected in a heavily industrialized area. The PFC levels in WWTP effluents were higher than those in surface waters with concentrations ranging from 18.4 to 41.1 ng/L for PFOA, and 1.69-3.85 ng/L for PFOS. Similar PFC profiles between effluents from WWTPs and urban surface waters were found. These results indicate that WWTPs are an important PFC source in surface water. Finally, we found that the composition profiles of PFCs in surface waters were similar to those in tap water, but not consistent with those in adult blood from Shenyang. The calculation on total daily intake of PFOS by adults from Shenyang showed that the contribution of drinking water to human exposure was minor.     

A study on pesticide runoff from paddy fields to a river in rural region--1: field survey of pesticide runoff in the Kozakura River, Japan

Runoff characteristics of nine kinds of herbicides from paddy fields were surveyed in the Kozakura River, that is one of the tributaries flowing into the Lake of Kasumigaura, over a period of 23 April to 30 June (before and after rice transplantation) of year. The flow rates of river water and the concentrations of herbicides in the river water were measured every day in May and every 2 days in April and June at six survey sites along the river. The runoff characteristics of herbicides were elucidated by taking account of the rainfall data, the detailed application data (application date and quantities of herbicides applied to each paddy field in a region), and their physico-chemical properties. The runoff rates (the runoff/application amounts ratio) were calculated for each herbicide, resulting in the range of 8.2-22.4%. The runoff rates were correlated fairly well with octanol-water partition coefficient, logP(ow), rather than with water solubility of herbicides.     

Prevalence and occurrence of zoonotic bacterial pathogens in surface waters determined by quantitative PCR

The prevalence and concentrations of Campylobacter jejuni, Salmonella spp. and enterohaemorrhagic Escherichia coli (EHEC) were investigated in surface waters in Brisbane, Australia using quantitative PCR (qPCR) based methodologies. Water samples were collected from Brisbane City Botanic Gardens (CBG) Pond, and two urban tidal creeks (i.e., Oxley Creek and Blunder Creek). Of the 32 water samples collected, 8 (25%), 1 (3%), 9 (28%), 14 (44%), and 15 (47%) were positive for C. jejuni mapA, Salmonella invA, EHEC O157 LPS, EHEC VT1, and EHEC VT2 genes, respectively. The presence/absence of the potential pathogens did not correlate with either E. coli or enterococci concentrations as determined by binary logistic regression. In conclusion, the high prevalence, and concentrations of potential zoonotic pathogens along with the concentrations of one or more fecal indicators in surface water samples indicate a poor level of microbial quality of surface water, and could represent a significant health risk to users. The results from the current study would provide valuable information to the water quality managers in terms of minimizing the risk from pathogens in surface waters.     

Occurrence and fate of organophosphorus flame retardants and plasticizers in urban and remote surface waters in Germany

Within this study, concentration levels and distribution of the organophosphates tris(2-chloroethyl) phosphate (TCEP), tris(2-chloro-1-methylethyl) phosphate (TCPP), tris(2-butoxyethyl) phosphate (TBEP), tri-iso-butyl phosphate (TiBP), and tri-n-butyl phosphate (TnBP) were investigated at nine lentic surface waters under different anthropogenic impact between June 2007 and October 2009. Furthermore, the possibility of in-lake photochemical degradation of the analytes was studied in laboratory experiments using spiked ultrapure water and lake water samples incubated in Teflon bottles (which transmit sunlight). TBEP, TiBP, and TnBP were photochemically degraded in spiked lake water samples upon exposure to sunlight. Organophosphate concentrations in the more remote lakes were often below or close to the limits of quantification (LOQ). TCPP was the substance with the highest median concentration in rural volcanic lakes (7-18 ng L⁻¹) indicating an atmospheric transport of the compound. At urban lakes their median concentrations were in the range of 23-61 ng L⁻¹ (TCEP), 85-126 ng L⁻¹ (TCPP), <LOQ-53 ng L⁻¹ (TBEP), 8-10 ng L⁻¹ (TiBP), and 17-32 ng L⁻¹ (TnBP). High variability but no significant seasonal trends were observed for all five organophosphates in urban lake water samples.