Impact of nitrogenous fertilizers on carbonate dissolution in small agricultural catchments: Implications for weathering CO2 uptake at regional and global scales

The goal of this study was to highlight the occurrence of an additional proton-promoted weathering pathway of carbonate rocks in agricultural areas where N-fertilizers are extensively spread, and to estimate its consequences on riverine alkalinity and uptake of CO2 by weathering. We surveyed 25 small streams in the calcareous molassic Gascogne area located in the Garonne river basin (south-western France) that drain cultivated or forested catchments for their major element compositions during different hydrologic periods. Among these catchments, the Hay and the Montousse´, two experimental catchments, were monitored on a weekly basis. Studies in the literature from other small carbonate catchments in Europe were dissected in the same way. In areas of intensive agriculture, the molar ratio (Ca + Mg)/HCO3 in surface waters is significantly higher (0.7 on average) than in areas of low anthropogenic pressure (0.5). This corresponds to a decrease in riverine alkalinity, which can reach 80% during storm events. This relative loss of alkalinity correlates well with the NO3 content in surface waters. In cultivated areas, the contribution of atmospheric/soil CO2 to the total riverine alkalinity (CO2 ATM-SOIL/HCO3) is less than 50% (expected value for carbonate basins), and it decreases when the nitrate concentration increases. This loss of alkalinity can be attributed to the substitution of carbonic acid (natural weathering pathway) by protons produced by nitrification of Nfertilizers (anthropogenic weathering pathway) occurring in soils during carbonate dissolution. As a consequence of these processes, the alkalinity over the last 30 years shows a decreasing trend in the Save river (one of the main Garonne river tributaries, draining an agricultural catchment), while the nitrate and calcium plus magnesium contents are increasing. We estimated that the contribution of atmospheric/soil CO2 to riverine alkalinity decreased by about 7–17% on average for all the studied catchments. Using these values, the deficit of CO2 uptake can be estimated as up to 0.22–0.53 and 12–29 Tg1 yr1 CO2 on a country scale (France) and a global scale, respectively. These losses represent up to 5.7–13.4% and only 1.6–3.8% of the total CO2 flux naturally consumed by carbonate dissolution, for France and on a global scale, respectively. Nevertheless, this loss of alkalinity relative to the Ca + Mg content relates to carbonate weathering by protons from N-fertilizers nitrification, which is a net source of CO2 for the atmosphere. This anthropogenic CO2 source is not negligible since it could reach 6–15% of CO2 uptake by natural silicate weathering and could consequently partly counterbalance this natural CO2 sink

Heavy metals partioning in three French forest soils by sequential extraction procedure

To know the concentration of heavy metal associated to chemical compounds is important to evaluate the environmental risks on soils, particularly regarding ion bioavailability. The relative mobility and strength of binding of heavy metals to the soil components can be studied using a sequential extraction procedure which provides a meaningful comparison between different soil profiles. The heavy metals partitioning bas been identified in three different french forest soils : one cambic podzol, one calcaric cambisol and one mollic andosol, using a new sequential extraction method. Results show that metal fractionation is metal and site specific. The water leaching phase does not contain any metals. The proportion of heavy metal leached in the exchangeable and the acid — soplhuabslee is significant for Cd. The residual phase is important for Cr, Pb, and to a lesser extend for Ni. The organic matter fraction is dominant for Zn and Cu. Thus, the considered heavy metals are mainly bounded to iron oxides, to the organic matter and to the mineral residue. The order of heavy metals availability in the three soils would be : Zn>Cd>Cu>Pb>NiL&egatd;C r.i sotopes in some extracts of the extraction procedure corroborate the anthropogenic inputs for two soils. These both infomations allow to trace the origin, the mobility and the distribution of Pb in the soil

Dissolved organic matter contribution to rain water, throughfall and soil solution chemistry

A method is proposed to determine the acidbase properties of natural water samples containing relatively high amounts of dissolved organic matter. The electroneutrality principle as well as titration data are used to estimate the organic anion concentration in open field precipitation, throughfall and soil solutions, and to develop empirical models based on pH and dissolved organic carbon content. The organic acids dissolved in throughfall have a similar acidic site density but are weaker than those dissolved in soil solution, stream and lake waters. This method is usefull to determine the contribution of organic anions to the charge balance and to the buffering capacity of dissolved organic rich waters with low acid neutralizing capacity. It can be used also to determine the respective contribution of natural organics and anthropogenic minerals to the total acidity of throughfall and rain waters

Modeling Acidification Recovery on Threatened Ecosystems: Application to the Evaluation of the Gothenburg Protocol in France

To evaluate the acid deposition reduction negotiated for 2010 within the UNECE LRTAP Gothenburg Protocol, sulphur and nitrogen deposition time-series (1880–2100) were compared to critical loads of acidity on five French ecosystems: Massif Central basalt (site 1) and granite (2); Paris Bassin tertiary sands (3); Vosges mountains sandstone (4) and Landes eolian sands (5). The SAFE model was used to estimate the response of soil solution pH and [A1] [BC] ratio to the deposition scenario. Among the five sites, critical loads were exceeded in the past at sites 3, 4 and 5. Sites 3 and 4 were still expected to exceed in 2010, the Protocol year. Further reduction of atmospheric deposition, mainly nitrogen, would be needed to achieve recovery on these ecosystems. At sites 3, 4 and 5, the delay between the critical load exceedance and the violation of the critical chemical criterion was estimated to be 10 to 30 years in the top soil and 50 to 90 years in the deeper soil. At site 5, a recovery was expected in the top soil in 2010 with a time lag of 10 years. Unexpectedly, soil pH continued to decrease after 1980 in the deeper soil at sites 2 and 5. This time lag indicated that acidification moved down the soil profile as a consequence of slow base cation depletion by ion exchange. This delayed response of the soil solution was the result of the combination of weathering rates and vegetation uptake but also of the relative ratio between base cation deposition and acid compounds

Metal contamination of soils and crops affected by the Chenzhou lead/zinc mine spill (Hunan, China)

In 1985, the collapse of the tailing dam in Chenzhou lead/zinc mine (Hunan, southern China) led to the spread of mining waste spills on the farmland along the Dong River. After the accident, an urgent soil cleaning up was carried out in some places. Seventeen years later, cereal (rice, maize, and sorghum), pulses (soybean, Adzuki bean, mung bean and peanut), vegetables (ipomoea, capsicum, taro and string bean) and the rooted soils were sampled at four sites: (1) the mining area (SZY), (2) the area still covered with the mining tailing spills (GYB), (3) the cleaned area from mining tailing spills (JTC), and (4) a background site (REF). Metal concentrations in the crops and soils were analyzed to evaluate the long-term effects of the spilled waste on the soil and the potential human exposure through food chains. The results showed that the physical–chemical properties of the soils obviously changed due to the different farming styles used by each individual farmer. Leaching effects and plant extraction of metals from some soils were quite weak. Certain soils were still heavily polluted with As, Cd, Zn, Pb and Cu. The contamination levels were in the order of GYB>SZY>JTC showing that the clean-up treatment was effective. The maximum allowable concentration (MAC) levels for Chinese agricultural soils were still highly exceeded, particularly for As and Cd (followed by Zn, Pb and Cu), with mean concentrations of 709 and 7.6 mg kg−1, respectively. These concentrations exceed the MAC levels by 24 times for As and 13 times for Cd at GYB. Generally, the edible leaves or stems of crops were more heavily contaminated than seeds or fruits. Ipomoea was the most severely contaminated crop. The concentrations of Cd and Pb were 3.30 and 76.9 mg kg−1 in ipomoea leaves at GYB, which exceeded the maximum permit levels (0.5 mg kg−1 for Cd and 9 mg kg−1 for Pb) by 6.6 and 8.5 times, respectively. Taro (+skin) could accumulate high concentrations of Zn and Cd in the edible stem, and rice and capsicum had high Cd concentration in the edible parts. However, the toxic element concentrations in maize, sorghum, Adzuki bean, soybean and mung bean remained lower than the threshold levels. The bio-accumulation factors (BAFs) of crops were in the order: Cd>Zn>Cu>Pb>As. BAF was typically lower in the edible seeds or fruits than in stems and leaves. The accumulation effect strongly depends on the crop's physiological properties, the mobility, of the metals, and the availability of metals in soils but not entirely on the total element concentrations in the soils. Even so, the estimated daily intake amount of Cu, Zn, Cd, and Pb from the crops grown in the affected three sites and arsenic at SZY and GYB exceeded the RDA (Recommended dietary allowance) levels. Subsequently, the crops grown in Chenzhou Pb/Zn mine waste affected area might have a hazardous effect on the consumer's health. This area still needs effective measures to cure the As, Cd, Pb, Zn and Cu contamination

Composition chimique des eaux et variabilité naturelle

La composition chimique d’une eau, avant toute perturbation anthropique,est contrôlée par son milieu environnemental (atmosphère, biosphère, sols et roches). En suivant le cycle de l’eau, depuis l’atmosphère vers les eaux continentales puis les océans,la concentration des eaux en éléments majeurs et traces et leur composition chimique changent grandement. Les précipitations atmosphériques sont faiblement concentrées en éléments majeurs (du μg/L au mg/L) et majoritairement composées de sodium (Na), de chlorure (Cl) et de sulfate (SO4), alors que les rivières et les nappes sont plus concentrées (10 à 102 mg/L) et composées surtout de calcium (Ca),de magnésium (Mg) et de bicarbonate(HCO3) (figure 1)

Localisation and mobility of trace metal in silver fir needles

Trace metals (TM: Co, Ni, Cu, Zn, Cd, and Pb) as well as Al, Mn, and Fe content was measured in needles of a remote silver fir stand in the south of France. TM localisation and behaviour in needles was evaluated by measuring total and internal content of needles of different ages. Measured concentrations fell within background values. Al, Fe, Co, and Pb were trapped in wax following atmospheric particulate deposition. Contrasting accumulation and migration behaviours of the different elements studied were observed. The wax contained less than 10% Mn, Al, Ni, Co, and Zn and 15–45% Fe, Cu, and Cd in the young needles. Lead was mostly located in the wax (50–80%), and this proportion decreased with needle age. Only the internal content of Pb and Fe increased significantly with needle age. Finally, due to atmospheric deposition accumulation, higher input fluxes of Fe, Cu, Cd, and Pb can be expected in forest soil

Soil heavy metal contamination and acid deposition: experimental approach on two forest soils in Hunan, Southern China

In 1985, a tailing dam collapsed in Hunan province (southern China) leading to soil contamination by heavy metals from the tailings waste. Moreover, acid deposition becomes more and more serious in this area. In this context, two forest soils (a red soil and a yellow red soil, typically and commonly found in southern China) were collected from Hunan. The objectives are (i) to determine releases and changes in speciation fractions of heavy metals (especially Cd, Cu, and Zn) when the soils are contaminated with heavy metals and affected by simulated acid deposition, and (ii) to study effects of soil heavy metals and acid deposition on releases of soil Ca2+, Mg2+, and Al3+. The soil samples were soaked in the solutions of CdCl2, CuCl2, and ZnCl2 for 15 days to make contaminated soils containing 200 mg kg1 of Cd, Cu, and Zn. Then the contaminated soils and the original soils were extracted with five simulated acid deposition solutions (pH ranged from 5.6 to 3.0 and total dissolved salts increased). The experimental results indicate that acid deposition leads to great releases of soil heavy metals due to complicated soil chemical processes, mostly cation exchange and partly dissolution of minerals at pH lower than 4.2. These released heavy metals come mainly from soil exchangeable pools and other labile fractions. Releases of heavy metals are closely controlled by pH values or, in some cases, total cation contents in acid deposition; meanwhile, concentrations of heavy metals are negatively related to the relevant pH values in soil equilibrium solutions when pH values are in a range of 4.2–5.1. From the point of view of heavy metal releases, Zn is the most sensitive to acid deposition, followed by Cd and Cu. Compared with the original soils, the contaminated soils could probably release more base cations Ca2+ and Mg2+ and less Al3+. Greater amounts of Cd, Cu, Zn, and Al released from Soil B show that this soil is more sensitive to acid deposition, and we could expect serious environmental contamination in Soil B area if mining activities and acid deposition are not under control in the future

Flood event impact on pesticide transfer in a small agricultural catchment (Moutousse at Aurade, south west France)

In this paper, pesticide transfer dynamic is studied during two flood events in a small experimental catchment close to Toulouse (south west France). Thirteen pesticide molecules (herbicides, fungicides) have been analysed by multi-residue technique on filtered and unfiltered waters. The results show very high pesticide concentrations in the different fractions compared to low flow periods and to the data collected by the French institutional networks in charge of the pesticide river water pollution survey. Several molecules present concentration higher than 0.1 mgL-1 and even higher than 1 mgL-1 in the unfiltered waters. In the suspended matters the concentrations vary respectively between 0.1 and 30 mg g-1 according to the molecules and can represent 40 to 90% of the total concentration for low soluble molecules. All the molecule concentrations and fluxes increase during the flood flows and have positive relationships with the stream discharge, but hysteresis between rising and falling periods can be observed for some molecules. Pesticide concentrations in unfiltered waters and partitioning between dissolved and particulate fractions (Kd¼[diss]/[part]) are controlled by dissolved organic carbon and total suspended matter. A good negative relationship can be established between logKd and logKow for 6 molecules