Pesticide pressure and fish farming in barrage pond in Northeastern France. Part II: residues of 13 pesticides in water, sediments, edible fish and their relationships

Residues of pesticides in fish farming productions from barrage ponds are seldom studied in spite of increasing health questionings and environmental concerns. The purpose of this study is to establish the pesticide contamination profiles of sediments and edible fish from five ponds in Northeastern France. Multi-residues method and liquid chromatography–tandem mass spectrometry analysis were used to quantify 13 pesticides (azoxystrobin, carbendazim, clomazone, diflufenican, dimethachlor, fluroxypyr, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl). Ten sediments and 143 muscles samples were analysed, corresponding to two successive fishing campaigns (first fishing date and second fishing date (P2), about 1 year later) on five sites (noted C-0, C-25, C-45, C-75 and C-85 to express the increasing gradient of crop area). Isoproturon was present in all sediments samples (1.8–56.4 μg/kg dry weight). During P2 period, carbendazim was quantified in the fish of site C-0 (0.09?±?0.02, 0.2?±?0.1 and 0.17?±?0.06 μg/kg wet weight (ww) for roach, carp and perch, respectively). Metazachlor was only quantified in perch of the site C-25 (0.13?±?0.02 μg/kg ww). Concentrations of isoproturon were similar for the sites C-45 and C-75 with 0.4?±?0.1 and 0.75?±?0.06 μg/kg ww for carp and perch, respectively. Contamination of fish reflected generally concentrations in surroundings. Isoproturon was the most concentrated and its main source was water for perch while carp was exposed through both water and sediments, highlighting their life strategies in pond.     

Effects of hydromorphology and riparian vegetation on the sediment quality of agricultural low-order streams: consequences for stream restoration

Intensive agricultural land use imposes multiple pressures on streams. More specifically, the loading of streams with nutrient-enriched soil from surrounding crop fields may deteriorate the sediment quality. The current study aimed to find out whether stream restoration may be an effective tool to improve the sediment quality of agricultural headwater streams. We compared nine stream reaches representing different morphological types (forested meandering reaches vs. deforested channelized reaches) regarding sediment structure, sedimentary nutrient and organic matter concentrations, and benthic microbial respiration. Main differences among reach types were found in grain sizes. Meandering reaches featured larger mean grain sizes (50–70 μm) and a thicker oxygenated surface layer (8 cm) than channelized reaches (40 μm, 5 cm). Total phosphorous amounted for up to 1,500 μg?g^?1 DW at retentive channelized reaches and 850–1,050 μg?g^?1 DW at the others. While N-NH₄ accumulated in the sediments (60–180 μg?g^?1 DW), N-NO₃ concentrations were generally low (2–5 μg?g^?1 DW). Benthic respiration was high at all sites (10–20 g O₂ m^?2?day^?1). Our study shows that both hydromorphology and bank vegetation may influence the sediment quality of agricultural streams, though effects are often small and spatially restricted. To increase the efficiency of stream restoration in agricultural landscapes, nutrient and sediment delivery to stream channels need to be minimized by mitigating soil erosion in the catchment.     

Landfill mining from a deposit of the chlorine/organochlorine industry as source of dioxin contamination of animal feed and assessment of the responsible processes

In 1997, the Polychlorinated dibenzo-para-dioxin (PCDD)/Polychlorinated dibenzofuran (PCDF) concentrations in dairy products in Germany and other European countries increased. The PCDD/PCDF source was contaminated lime used in Brazilian citrus pulp pellets. The contaminated lime was mined from an industrial dump site. However, the detailed origin of the PCDD/PCDFs in the lime was not revealed. This paper investigates the contamination origin and describes the link between lime milk from the dumpsite of a chlorine/organochlorine industry and the contaminated lime. The contaminated lime stem from mining at the corporate landfill of Solvay Indupa in Sao Paulo. The landfill was used for 40 years for deposition of production residues and closed in 1996. The factory operated/operates at least two processes with potentially high PCDD/PCDFs releases namely the oxychlorination process for production of ethylene dichloride (EDC) and the chlor-alkali process. The main landfilled waste was lime milk (1.4 million tons) from the vinyl chloride monomer production (via the acetylene process) along with residues from other processes. The PCDD/PCDF fingerprint revealed that most samples from the chemical landfill showed an EDC PCDD/PCDF pattern with a characteristic octachlorodibenzofuran dominance. The PCDD/PCDF pattern of a Rio Grande sediment samples downstream the facility showed a chlor-alkali pattern with a minor impact of the EDC pattern. The case highlights that PCDD/PCDF- and persistent organic pollutants-contaminated sites need to be identified in a comprehensive manner as required by the Stockholm Convention (article 6) and controlled for their impact on the environment and human health. Landfill mining and reuse of materials from contaminated deposits should be prohibited.     

Approximation and spatial regionalization of rainfall erosivity based on sparse data in a mountainous catchment of the Yangtze River in Central China

In densely populated countries like China, clean water is one of the most challenging issues of prospective politics and environmental planning. Water pollution and eutrophication by excessive input of nitrogen and phosphorous from nonpoint sources is mostly linked to soil erosion from agricultural land. In order to prevent such water pollution by diffuse matter fluxes, knowledge about the extent of soil loss and the spatial distribution of hot spots of soil erosion is essential. In remote areas such as the mountainous regions of the upper and middle reaches of the Yangtze River, rainfall data are scarce. Since rainfall erosivity is one of the key factors in soil erosion modeling, e.g., expressed as R factor in the Revised Universal Soil Loss Equation model, a methodology is needed to spatially determine rainfall erosivity. Our study aims at the approximation and spatial regionalization of rainfall erosivity from sparse data in the large (3,200 km²) and strongly mountainous catchment of the Xiangxi River, a first order tributary to the Yangtze River close to the Three Gorges Dam. As data on rainfall were only obtainable in daily records for one climate station in the central part of the catchment and five stations in its surrounding area, we approximated rainfall erosivity as R factors using regression analysis combined with elevation bands derived from a digital elevation model. The mean annual R factor (R _a) amounts for approximately 5,222 MJ?mm?ha^?1?h^?1?a^?1. With increasing altitudes, R _a rises up to maximum 7,547 MJ?mm ha^?1?h^?1 a^?1 at an altitude of 3,078 m a.s.l. At the outlet of the Xiangxi catchment erosivity is at minimum with approximate R _a?=?1,986 MJ?mm?ha^?1?h^?1?a^?1. The comparison of our results with R factors from high-resolution measurements at comparable study sites close to the Xiangxi catchment shows good consistance and allows us to calculate grid-based R _a as input for a spatially high-resolution and area-specific assessment of soil erosion risk.     

Effects of riparian forest buffers on in-stream nutrient retention in agricultural catchments

In northeastern Austria, marshlands have been turned into the most productive arable land of the country. As a result, most headwater streams show structurally degraded channels, lacking riparian buffer zones, which are heavily loaded with nutrients from the surrounding crop fields. The present study examines whether longitudinally restricted riparian forest buffers can enhance the in-stream nutrient retention in nutrient-enriched headwater streams. We estimated nutrient uptake from pairwise, short-term addition experiments with NH, NH, PO, and NaCl within reaches with riparian forest buffers (RFB) and degraded reaches (DEG) of the same streams. Riparian forest buffers originated from the conservation of the pristine vegetation or from restoration measures. Hydrologic retention was calculated with the model OTIS-P on the basis of conductivity break-through curves from the salt injections. A significant increase in surface transient storage was revealed in pristine and restored RFB reaches compared with DEG reaches due to the longitudinal step-pool pattern and the frequent occurrence of woody debris on the channel bed. Ammonium uptake lengths were significantly shorter in RFB reaches than in DEG reaches, resulting from the higher hydrologic retention. Uptake velocities did not differ significantly between RFB and DEG reaches, indicating that riparian forest buffers did not affect the biochemical nutrient demand. Uptake of NH was mainly driven by autotrophs. Net PO uptake was not affected by riparian forest buffers. The study shows that the physical and biogeochemical effects of riparian forest buffers on the in-stream nutrient retention are limited in the case of highly eutrophic streams.     

Strontium isotope study of coal utilization by-products interacting with environmental waters

Sequential leaching experiments on coal utilization by-products (CUB) were coupled with chemical and strontium (Sr) isotopic analyses to better understand the influence of coal type and combustion processes on CUB properties and the release of elements during interaction with environmental waters during disposal. Class C fly ash tended to release the highest quantity of minor and trace elements-including alkaline earth elements, sodium, chromium, copper, manganese, lead, titanium, and zinc-during sequential extraction, with bottom ash yielding the lowest. Strontium isotope ratios ((87)Sr/(86)Sr) in bulk-CUB samples (total dissolution of CUB) are generally higher in class F ash than in class C ash. Bulk-CUB ratios appear to be controlled by the geologic source of the mineral matter in the feed coal, and by Sr added during desulfurization treatments. Leachates of the CUB generally have Sr isotope ratios that are different than the bulk value, demonstrating that Sr was not isotopically homogenized during combustion. Variations in the Sr isotopic composition of CUB leachates were correlated with mobility of several major and trace elements; the data suggest that arsenic and lead are held in phases that contain the more radiogenic (high-(87)Sr/(86)Sr) component. A changing Sr isotope ratio of CUB-interacting waters in a disposal environment could forecast the release of certain strongly bound elements of environmental concern. This study lays the groundwork for the application of Sr isotopes as an environmental tracer for CUB-water interaction.     

Simulating Land-Cover Change in Montane Mainland Southeast Asia

We used the conversion of land use and its effects (CLUE-s) model to simulate scenarios of land-cover change in Montane mainland southeast Asia (MMSEA), a region in the midst of transformation due to rapid intensification of agriculture and expansion of regional trade markets. Simulated changes affected approximately 10 % of the MMSEA landscape between 2001 and 2025 and 16 % between 2001 and 2050. Roughly 9 % of the current vegetation, which consists of native species of trees, shrubs, and grasses, is projected to be replaced by tree plantations, tea, and other evergreen shrubs during the 50 years period. Importantly, 4 % of this transition is expected to be due to the expansion of rubber (Hevea brasiliensis), a tree plantation crop that may have important implications for local-to-regional scale hydrology because of its potentially high water consumption in the dry season.     

Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Empirical models based on the universal soil loss equation fail to predict sediment discharges from Chesapeake Bay catchments

The Universal Soil Loss Equation (USLE) and its derivatives are widely used for identifying watersheds with a high potential for degrading stream water quality. We compared sediment yields estimated from regional application of the USLE, the automated revised RUSLE2, and five sediment delivery ratio algorithms to measured annual average sediment delivery in 78 catchments of the Chesapeake Bay watershed. We did the same comparisons for another 23 catchments monitored by the USGS. Predictions exceeded observed sediment yields by more than 100% and were highly correlated with USLE erosion predictions (Pearson r range, 0.73-0.92; p < 0.001). RUSLE2-erosion estimates were highly correlated with USLE estimates (r = 0.87; p < 001), so the method of implementing the USLE model did not change the results. In ranked comparisons between observed and predicted sediment yields, the models failed to identify catchments with higher yields (r range, -0.28-0.00; p > 0.14). In a multiple regression analysis, soil erodibility, log (stream flow), basin shape (topographic relief ratio), the square-root transformed proportion of forest, and occurrence in the Appalachian Plateau province explained 55% of the observed variance in measured suspended sediment loads, but the model performed poorly (r(2) = 0.06) at predicting loads in the 23 USGS watersheds not used in fitting the model. The use of USLE or multiple regression models to predict sediment yields is not advisable despite their present widespread application. Integrated watershed models based on the USLE may also be unsuitable for making management decisions.     

Life cycle assessment of waste paper management: The importance of technology data and system boundaries in assessing recycling and incineration

The significance of technical data, as well as the significance of system boundary choices, when modelling the environmental impact from recycling and incineration of waste paper has been studied by a life cycle assessment focusing on global warming potentials. The consequence of choosing a specific set of data for the reprocessing technology, the virgin paper manufacturing technology and the incineration technology, as well as the importance of the recycling rate was studied. Furthermore, the system was expanded to include forestry and to include fossil fuel energy substitution from saved biomass, in order to study the importance of the system boundary choices. For recycling, the choice of virgin paper manufacturing data is most important, but the results show that also the impacts from the reprocessing technologies fluctuate greatly. For the overall results the choice of the technology data is of importance when comparing recycling including virgin paper substitution with incineration including energy substitution. Combining an environmentally high or low performing recycling technology with an environmentally high or low performing incineration technology can give quite different results. The modelling showed that recycling of paper, from a life cycle point of view, is environmentally equal or better than incineration with energy recovery only when the recycling technology is at a high environmental performance level. However, the modelling also showed that expanding the system to include substitution of fossil fuel energy by production of energy from the saved biomass associated with recycling will give a completely different result. In this case recycling is always more beneficial than incineration, thus increased recycling is desirable. Expanding the system to include forestry was shown to have a minor effect on the results. As assessments are often performed with a set choice of data and a set recycling rate, it is questionable how useful the results from this kind of LCA are for a policy maker. The high significance of the system boundary choices stresses the importance of scientific discussion on how to best address system analysis of recycling, for paper and other recyclable materials.