Stream chemical dynamic and metal accumulation in a temperate watershed affected by agricultural practices (Penzé, NW France).

RATIONALE: Understanding the fate of metals in agricultural land is an important issue for agronomic sustainability. This study aimed at quantifying the export/retention of metals in a temperate watershed subject to important manuring activities. METHODS: The chemical composition of the Penzé stream was examined at high resolution during a 1-year study in 2012. After immediate on-site filtration, here demonstrated as necessary to avoid modification of the dissolved-particulate partition, the concentrations of 21 elements were determined using inductively coupled plasma (ICP) optical emission spectrometry and ICP mass spectrometry. This dataset was extended with the local atmospheric deposition of several metals (Cd, Cr, Cu, Pb, Ni and Zn) monitored on a monthly basis. RESULTS: Two groups were distinguished according to the evolution of the concentrations during floods. Some major cations (Na, Ca, Mg, Sr, K, Ba) and nitrate followed counter-clockwise hysteresis patterns originating from the dilution of the enriched groundwaters by surface waters. Conversely, Al, Fe, Mn, Ti, V, Cr, Co, Ni, Cu, Zn, Cd, Pb and U displayed high dissolved concentration increases at the early stage of floods due to washing out of the enriched soils. CONCLUSIONS: The comparison of stream output fluxes for the two main inputs for the watershed, i.e. atmospheric deposition and manure spreading, indicates that the vast majority of the Cu and Zn (>99 and 96%, respectively), mainly originating from pig manure, is accumulated in the watershed. The accumulation rates for other metals were >60% for Ni and Cr, >75% for As and >90% for Pb and Cd.

Dynamics and sources of reduced sulfur, humic substances and dissolved organic carbon in a temperate river system affected by agricultural practices.

Although reduced organic sulfur substances (RSS) as well as humic substances (HS) are widely suspected to play a role in, for example, metal speciation or used as a model of dissolved organic carbon (DOC) in laboratory studies, reports of their quantification in natural waters are scarce. We have examined the dynamics and sources of reduced sulfur, HS and DOC over an annual cycle in a river system affected by agricultural practices. The new differential pulse cathodic stripping voltammetry was successfully applied to measure glutathione-like compounds (GSHs), thioacetamide-like compounds (TAs) and the liquid chromatography coupled to organic detector to analyze HS and DOC at high frequency in the Penzé River (NW France). The streamflow-concentration patterns, principal components analysis and flux analysis allowed discrimination of the source of each organic compound type. Surprisingly, the two RSS and HS detected in all samples, displayed different behavior. As previously shown, manuring practice is the main source of DOC and HS in this watershed where agricultural activity is predominant. The HS were then transferred to the river systems via runoff, particularly during the spring and autumn floods, which are responsible of >60% of the annual flux. TAs had a clear groundwater source and may be formed underground, whereas GSHs displayed two sources: one aquagenic in spring and summer probably linked to the primary productivity and a second, which may be related to bacterial degradation. High sampling frequency allowed a more accurate assessment of the flux values which were 280 tC y(-1) for DOC representing 20 kg C ha(-1) y(-1). HS, TAs and GSHs fluxes represented 60, 13, and 4% of the total annual DOC export, respectively.

Elimination of polar micropollutants and anthropogenic markers by wastewater treatment in Beijing, China.

Anthropogenic contamination of surface waters in Asia is on the increase. While polar organic contaminants are gradually recognized for their impacts on aquatic ecosystems in the Western World, less is known about the situation in Asia. In developing countries like China, water resources are particularly vulnerable. We investigated the occurrence, elimination, and per capita loads of a wide range of pharmaceuticals, household chemicals and pesticides in five Beijing WWTPs representative for megacities in China, and compare the efficiency of different treatment processes. Based on initial screening for 268 micropollutants using high-resolution mass spectrometry, 33 compounds were examined in detail. Pollutant concentrations in raw wastewater ranged from <0.02 µg L(-1) for pesticides to >20 µg L(-1) for caffeine and the contrast agent iopromide. Concentrations in the WWTP effluents were generally <1 µg L(-1), except for some pharmaceuticals, iopromide (1.2-18 µg L(-1)), caffeine (0.025-2.3 µg L(-1)), and the artificial sweetener sucralose (2.7-3.5 µg L(-1)). Elimination efficiencies varied greatly from <1% to close to 100%, with macrolides, some sulfonamides, metronidazole, iopromide, and 4-acetamidoantipyrine being the most persistent compounds. Total per capita loads of the investigated micropollutants were lower than in communal wastewater of Europe, amounting to 7.9-12.2 and 2.0-6.5 g d(-1)1000 inhabitants(-1) in the influents and effluents, respectively, with an average release of ∼100 kg d(-1) by the 11.4 million people and 2.3 million m(3) of wastewater treated per day. Since the wastewater effluents are often used for agricultural irrigation, residual organic pollutants pose a threat to food safety, the development of antibacterial resistance, and combined effects of micropollutants in the aquatic environment.

Implications of effluent organic matter and its hydrophilic fraction on zinc(II) complexation in rivers under strong urban pressure: aromaticity as an inaccurate indicator of DOM-metal binding.

The zinc binding characteristics of dissolved organic matter (DOM) fractions from the Seine River Basin were studied after being separated and extracted according to their polarity: hydrophobic, transphilic, and hydrophilic. The applied experimental methodology was based on a determination of labile zinc species by means of differential pulse anodic stripping voltammetry (DPASV) at increasing concentrations of total zinc on a logarithmic scale and at fixed levels of: pH, ionic strength, and temperature. Fitting the DOM fractions with two discrete classes of ligands successfully allowed determining the conditional zinc binding constants (Ki) as well as total ligand density (LiT). The binding constants obtained for each DOM fraction were then compared and discussed with respect to the hydrophobic/hydrophilic nature and sample origin. Results highlighted a strong complexation of zinc to the effluent organic matter and especially the most hydrophilic fraction, which also displayed a very low specific UV absorbance. Although the biotic ligand model takes into account the quality of DOM through UV absorbance in the predictions of metal bioavailability and toxicity, this correction is not efficient for urban waters.

Organic micropollutants in the Yangtze River: seasonal occurrence and annual loads.

Twenty percent of the water run-off from China's land surface drains into the Yangtze River and carries the sewage of approximately 400 million people out to sea. The lower stretch of the Yangtze therefore offers the opportunity to assess the pollutant discharge of a huge population. To establish a comprehensive assessment of micropollutants, river water samples were collected monthly from May 2009 to June 2010 along a cross-section at the lowermost hydrological station of the Yangtze River not influenced by the tide (Datong Station, Anhui province). Following a prescreening of 268 target compounds, we examined the occurrence, seasonal variation, and annual loads of 117 organic micropollutants, including 51 pesticides, 43 pharmaceuticals, 7 household and industrial chemicals, and 16 polycyclic aromatic hydrocarbons (PAHs). During the 14-month study, the maximum concentrations of particulate PAHs (1-5 µg/g), pesticides (11-284 ng/L), pharmaceuticals (5-224 ng/L), and household and industrial chemicals (4-430 ng/L) were generally lower than in other Chinese rivers due to the dilution caused of the Yangtze River's average water discharge of approximately 30,000 m(3)/s. The loads of most pesticides, anti-infectives, and PAHs were higher in the wet season compared to the dry season, which was attributed to the increased agricultural application of chemicals in the summer, an elevated water discharge through the sewer systems and wastewater treatment plants (WWTP) as a result of high hydraulic loads and the related lower treatment efficiency, and seasonally increased deposition from the atmosphere and runoff from the catchment. The estimated annual load of PAHs in the river accounted for some 4% of the total emission of PAHs in the whole Yangtze Basin. Furthermore, by using sucralose as a tracer for domestic wastewater, we estimate a daily disposal of approximately 47 million m(3) of sewage into the river, corresponding to 1.8% of its average hydraulic load. In summary, the annual amounts flushed by the Yangtze River into the East China Sea were 2.9×10(6)tons of dissolved and particulate organic carbon (DOC and POC), 369 tons of PAHs, 98 tons of pesticides, 152 tons of pharmaceuticals, and 273 tons of household and industrial chemicals. While the concentrations seem comparably moderate, the pollutant loads are considerable and pose an increasing burden to the health of the marine coastal ecosystem.

Simple and simultaneous determination of glutathione, thioacetamide and refractory organic matter in natural waters by DP-CSV.

Although reduced sulphur substances, such as thiol compounds, contain extremely reactive functional groups in the cell, and influence metal speciation and solubility, very few techniques have been developed to quantify such substances in natural waters. In this paper we present a novel method that allows for the simultaneous identification and quantification of glutathione (GSH), thioacetamide-like compounds (TA), and refractory organic matter (ROM) by differential pulse cathodic stripping voltammetry (DP-CSV). Organic compounds are initially deposited on a mercury drop electrode at 0.000 V, pH 1.95, in the presence of ~200 nmol L(-1) Mo(VI), and then stripped, creating reduction peak currents at specific potentials. Using a 60-s deposition time, limits of detection (LODs) are 1 nmol L(-1), 81 nmol L(-1) and 14 µg C L(-1) for GSH, TA and ROM, respectively. By increasing the deposition time to 300 s, LOD is decreased to 0.2 nmol L(-1), 22 nmol L(-1) and 2 µg C L(-1), respectively. This method has a number of advantages in terms of its rapidity, low cost, and relative simplicity (due to the lack of derivatization and pre-concentration steps) and is also an effective method for simultaneously analysing GSH, TA and ROM in water. When not mixed in solution, GSH, L-cysteine and N-acetyl-L-cysteine, as well as TA-like compounds and thiourea, can be detected and identified by measuring their peak potential and standard addition, due to the acidic pH, which also allows for a longer preservation of the filtered sample. The new method described in this paper was tested along an entire river-seawater gradient of the Aulne Estuary (Brittany, France) to assess its capability in terms of determining these natural organic compounds in various surface waters.

Polycyclic aromatic hydrocarbons in wastewater, WWTPs effluents and in the recipient waters of Beijing, China.

In this study, surface water samples from the Wenyu River and the North Canal, effluent from major wastewater treatment plants (WWTPs) in Beijing, and wastewater from open sewers that discharge directly into the river system were collected and analyzed for 16 priority USEPA polycyclic aromatic hydrocarbons (PAHs). Concentrations of these 16 PAHs ranged from 193 to 1790 ng/L in river surface waters, 245 to 404 ng/L in WWTP effluents, and 431 to 2860 ng/L in the wastewater from the small sewers. The WWTP effluent was the main contributor of dissolved PAHs to the river, while wastewater from the small sewers contributed both dissolved and suspended particulate matter-associated PAH to the river as indicated by the high dissolved organic carbon and suspended particulate matter contents in the wastewater. Although the flow from each open sewer was small, a PAH discharge as high as 44 kg/year could occur into the river from these types of sewers. This amount was equivalent to about 22 % of the PAH loads discharged into the North Canal downstream from Beijing, whereas the remainder was mainly released by the major WWTPs in Beijing.

Organic micropollutants in rivers downstream of the megacity Beijing: sources and mass fluxes in a large-scale wastewater irrigation system.

The Haihe River System (HRS) drains the Chinese megacities Beijing and Tianjin, forming a large-scale irrigation system severely impacted by wastewater-borne pollution. The origin, temporal magnitudes, and annual mass fluxes of a wide range of pharmaceuticals, household chemicals, and pesticides were investigated in the HRS, which drains 70% of the wastewater discharged by 20 million people living in Beijing. Based on Chinese consumption statistics and our initial screening for 268 micropollutants using high-resolution mass spectrometry, 62 compounds were examined in space and time (2009-2010). The median concentrations ranged from 3 ng/L for metolachlor to 1100 ng/L for benzotriazole and sucralose. Concentrations of carbendazim, clarithromycin, diclofenac, and diuron exceed levels of ecotoxicological concern. Mass-flux analyses revealed that pharmaceuticals (5930 kg/year) and most household chemicals (5660 kg/year) originated from urban wastewaters, while the corrosion inhibitor benzotriazole entered the rivers through other pathways. Total pesticide residues amounted to 1550 kg/year. Per capita loads of pharmaceuticals in wastewater were lower than those in Europe, but are expected to increase in the near future. As 95% of the river water is diverted to irrigate agricultural soil, the loads of polar organic micropollutants transported with the water might pose a serious threat to food safety and groundwater quality.

Sources and pathways of nutrients in the semi-arid region of Beijing-Tianjin, China.

Semiarid regions worldwide are particularly prone to eutrophication, which causes immense ecological and economic problems. One region that is in transition and requires systematic research for effective intervention is the dry landscape of Beijing-Tianjin (P. R. China). We investigated the sources and spatiotemporal loads of nitrogen and phosphorus species over a one-year period in the Haihe catchment that drains the megacity of Beijing. Although wastewater treatment was improved in recent years, the rivers were heavily contaminated by 0.3-5.3 mg P L(-1) and 3.0-49 mg N L(-1), with toxic levels of nitrite (≥1 mg NO(2)-N L(-1)) and ammonia (≥0.6 mg NH(3)-N L(-1)). The average NH(4)(+) (16.9 mg N L(-1)) increased by 160% compared to 1996-levels. Mass fluxes and δ(15)N-signatures revealed that nutrients originated almost exclusively from sewage. Furthermore, the water balance demonstrated that >90% of the polluted river water was diverted for irrigation, thereby threatening food safety and groundwater quality. Per capita loads of 1.42 kg N/yr and 115 g P/yr were comparable to the peak discharges typical of Europe and the United States in 1970-1990, but concentrations were 2-3 times higher in the Beijing-Tianjin region. Our research identified sewage as the predominant nutrient source in this semiarid region, which suggests that state-of-the-art wastewater treatment would drastically mitigate eutrophication and even more rapidly than was previously observed in Europe.

Dissolved organic matter from treated effluent of a major wastewater treatment plant: characterization and influence on copper toxicity.

A combination of reverse osmosis (RO) concentration and DAX-8/XAD-4 resin adsorption techniques is used to isolate the various constituents of urban dissolved organic matter (DOM) from inorganic salts. Three fractions: hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) accounting respectively for 35%, 20% and 45% of extracted carbon, are isolated from effluents of a major French wastewater treatment plant. This atypical DOC distribution, in comparison with natural water where the HPO fraction dominates, shows the significance of HPI fraction which often gets neglected because of extraction difficulties. A number of analytical techniques (elemental, spectroscopic: UV, FTIR) allow highlighting the weak aromaticity of wastewater effluent DOM (EfOM) due to fewer degradation and condensation processes and the strong presence of proteinaceous structures indicative of intense microbial activity. Copper toxicity in the presence of DOM is estimated using an acute toxicity test on Daphnia Magna (Strauss). Results reveal the similar protective role of each EfOM fraction compared to reference Suwannee river fulvic acid despite lower EfOM aromaticity (i.e. specific UV absorbance). The environmental implications of these results are discussed with respect to the development of site-specific water quality criteria.

Dissolved iron analysis in estuarine and coastal waters by using a modified adsorptive stripping chronopotentiometric (SCP) method.

An electrochemical method based on adsorptive stripping chronopotentiometry (SCP) with a rotating mercury film electrode has been developed for the determination of dissolved iron (III) at subnanomolar concentrations in estuarine and coastal waters. The detection limit was 0.11 nM after adsorption time of 60s. Compared to the other chronopotentiometric methods available for dissolved iron measurement in natural and estuarine waters, the procedure described here exhibits a 15-fold better sensitivity. Therefore, it allows one to accurately quantify concentrations commonly found in estuarine and coastal waters. Moreover, by using the speciation scheme proposed by Aldrich and van den Berg (Electroanalysis 10 (1998) 369), several forms could be measured, i.e. reactive iron (Fe R) and reactive iron (III) (Fe(III) R), or estimated, i.e. complexed iron (Fe C) and reactive iron (II) (Fe(II) R). The method described here is reliable, fast, inexpensive and compact. It was applied successfully to the study of the chemical speciation of dissolved iron along the salinity gradient of the Aulne estuary (Brittany-France).

Determination of dissolved iron(III) in estuarine and coastal waters by adsorptive stripping chronopotentiometry (SCP).

An adsorptive stripping chronopotentiometric (SCP) method has been developed for quantification of dissolved iron in estuarine and coastal waters. After UV-digestion of filtered samples the Fe(III) ions in non-deoxygenated samples were complexed with solochrom violet RS (SVRS). The complexes were then accumulated by adsorption on the surface of a mercury-film electrode. The stripping step was performed by applying a constant current of -17 microA. Sensitivity and detection limit were 15 ms nmol(-1) L (270 ms microg(-1) L) and 1.5 nmol L(-1) (84 ng L(-1)), respectively, for 60-s electrolysis time. Compared with the only other chronopotentiometric method available for measurement of iron in natural waters, our procedure is fifty times more sensitive in a quarter of the electrolysis time. It therefore enables detection of the concentrations currently found in estuarine and coastal waters. The method was successfully used to study the behaviour and seasonal variations of dissolved iron in the Penzé estuary, NW France.