Sulphur transformation and deposition in the rhizosphere of Juncus effusus in a laboratory-scale constructed wetland

Sulphur cycling and its correlation to removal processes under dynamic redox conditions in the rhizosphere of helophytes in treatment wetlands are poorly understood. Therefore, long-term experiments were performed in laboratory-scale constructed wetlands treating artificial domestic wastewater in order to investigate the dynamics of sulphur compounds, the responses of plants and nitrifying microorganisms under carbon surplus conditions, and the generation of methane. For carbon surplus conditions (carbon:sulphate of 2.8:1) sulphate reduction happened but was repressed, in contrast to unplanted filters mentioned in literature. Doubling the carbon load caused stable and efficient sulphate reduction, rising of pH, increasing enrichment of S(2-) and S(0) in pore water, and finally plant death and inhibition of nitrification by sulphide toxicity. The data show a clear correlation of the occurrence of reduced S-species with decreasing C and N removal performance and plant viability in the experimental constructed wetlands.     

Variation of MCPA, metribuzine, methyltriazine-amine and glyphosate degradation, sorption, mineralization and leaching in different soil horizons

Pesticide mineralization and sorption were determined in 75 soil samples from 15 individually drilled holes through the vadose zone along a 28 km long transect of the Danish outwash plain. Mineralization of the phenoxyacetic acid herbicide MCPA was high both in topsoils and in most subsoils, while metribuzine and methyltriazine-amine was always low. Organic matter and soil pH was shown to be responsible for sorption of MCPA and metribuzine in the topsoils. The sorption of methyltriazine-amine in topsoil was positively correlated with clay and negatively correlated with the pH of the soil. Sorption of glyphosate was tested also high in the subsoils. One-dimensional MACRO modeling of the concentration of MCPA, metribuzine and methyltriazine-amine at 2 m depth calculated that the average concentration of MCPA and methyltriazine-amine in the groundwater was below the administrative limit of 0.1 μg/l in all tested profiles while metribuzine always exceeded the 0.1 μg/l threshold value.     

Spatial variability of arsenic concentration in soils and plants, and its relationship with iron, manganese and phosphorus

Spatial distribution of arsenic (As) concentrations of irrigation water, soil and plant (rice) in a shallow tube-well (STW) command area (8 ha), and their relationship with Fe, Mn and P were studied. Arsenic concentrations of water in the 110 m long irrigation channel clearly decreased with distance from the STW point, the range being 68-136 μg L⁻¹. Such decreasing trend was also noticed with Fe and P concentrations, but the trend for Mn concentrations was not remarkable. Concerning soil As, the concentration showed a decreasing tendency with distance from the pump. The NH₄-oxalate extractable As contributed 36% of total As and this amount of As was associated with poorly crystalline Fe-oxides. Furthermore only 22% of total As was phosphate extractable so that most of the As was tightly retained by soil constituents and was not readily exchangeable by phosphate. Soil As (both total and extractable As) was significantly and positively correlated with rice grain As (0.296 ± 0.063 μg g⁻¹, n = 56). Next to drinking water, rice could be a potential source of As exposure of the people living in the As affected areas of Bangladesh.     

In field arsenic removal from natural water by zero-valent iron assisted by solar radiation

An in situ arsenic removal method applicable to highly contaminated water is presented. The method is based in the use of steel wool, lemon juice and solar radiation. The method was evaluated using water from the Camarones River, Atacama Desert in northern Chile, in which the arsenic concentration ranges between 1000 and 1300 μg L⁻¹. Response surface method analysis was used to optimize the amount of zero-valent iron (steel wool) and the citrate concentration (lemon juice) to be used. The optimal conditions when using solar radiation to remove arsenic from natural water from the Camarones river are: 1.3 g L⁻¹ of steel wool and one drop (ca. 0.04 mL) of lemon juice. Under these conditions, removal percentages are higher than 99.5% and the final arsenic concentration is below 10 μg L⁻¹. This highly effective arsenic removal method is easy to use and inexpensive to implement.     

Long term changes in atmospheric N and S throughfall deposition and effects on soil solution chemistry in a Scots pine forest in the Netherlands

In a Scots pine forest the throughfall deposition and the chemical composition of the soil solution was monitored since 1984. (Inter)national legislation measures led to a reduction of the deposition of nitrogen and sulphur. The deposition of sulphur has decreased by approximately 65%. The total mineral-nitrogen deposition has decreased by ca. 25%, which is mainly due to a reduction in ammonium-N deposition (−40%), since nitrate-N deposition has increased (+50%). The nitrogen concentration in the upper mineral soil solution at 10 cm depth has decreased, leading to an improved nutritional balance, which may result in improved tree vitality. In the drainage water at 90 cm depth the fluxes of NO₃⁻ and SO₄²⁻ have decreased, resulting in a reduced leeching of accompanying base cations, thus preserving nutrients in the ecosystem. It may take still several years, however, before this will meet the prerequisite of a sustainable ecosystem.     

Diffusion pollution from livestock and poultry rearing in the Yangtze Delta,China

BACKGROUND: The Yangtze Delta is one of the most developed regions in China and includes Shanghai, eight cities in Jiangsu province and eight cities in Zhejiang province. Meat consumption in this region has increased with economic growth, and most of the consumed meat is produced locally. The water quality of surface waters has deteriorated in recent years. An example was the huge blue-green algae bloom in Tai Lake in late May 2007, which affected millions of people's daily drinking water. However, animal husbandry is considered to be one of the main pollution sources. METHODS: Pollutants (NH3-N, total phosphorus (TP), and total nitrogen (TN)) excreted by livestock and poultry, and the resultant COD (chemical oxygen demand) and BOD (biochemical oxygen demand), were estimated using two different methods based on different data sets. RESULTS: The number of livestock and poultry has remained stable in the Yangtze Delta over the four years from 1999 to 2002, with the average number of pigs, cattle, sheep and poultry being 21.1 M, 0.4 M, 7.7 M and 597.6 M, respectively. Pollutants in livestock and poultry excreta estimated by Method I were: 0.12 Mt NH3-N, 0.11 Mt TP and 0.29 Mt TN, resulting in COD and BOD of 1.34 Mt and 1.30 Mt, respectively, while the estimations based on Method II were: 0.18 Mt NH3-N, 0.15 Mt TP and 0.40 Mt TN, resulting in COD and BOD of 1.95 Mt and 1.80 Mt, respectively. DISCUSSION: Pollutants excreted annually by livestock and poultry in the Yangtze Delta are estimated to be: 0.17 Mt NH3-N, 0.16 Mt TP and 0.42 Mt TN, giving rise to a COD of 1.86 Mt and a BOD of 1.72 Mt. Approximately 25% of this pollution was estimated to enter water bodies, which means that the annual pollutant load is 43,700 t NH3-N, 39,400 tTP, 104,600t TN with a COD of 465,000 tand a BOD of 430,100 t. Pollutants from animal husbandry were similar in magnitude to those from industrial wastewater. Pigs produced the most pollution, followed by poultry, cattle and sheep. The pollution load from animal husbandry in the Yangtze Delta is about twice the average level of the whole of China. CONCLUSIONS: Domestic wastewater was the main pollution source in the Yangtze Delta, followed by pollution from raising livestock and poultry and from industrial wastewater. The pollution load in Shanghai and Jiaxing were the greatest, followed by 7 cities of Jiangsu province (except Suzhou) and other cities of Zhejiang province and Suzhou. Pigs and poultry produced about 90% of the total pollutants from animal husbandry. RECOMMENDATIONS AND PERSPECTIVES: The local governments, especially in Shanghai and Jiaxing, should focus their attention on the pollution produced by livestock and poulrry. Controlling pollution from pigs and poultry will have the greatest impact in this region. Control of pollution will be facilitated by the development of large-scale livestock and poultry farming units and a shift away from small scale husbandry.     

Dioxins,chlorophenols and other chlorinated organic pollutants in colloidal and water fractions of groundwater from a contaminated sawmill site

BACKGROUND, AIM, AND SCOPE: The distribution of chlorinated organic contaminants in groundwater and the importance of colloids were studied in groundwater from a sawmill site contaminated by chlorophenol preservatives. MATERIALS AND METHODS: The groundwater was fractionated into three different size ranges: (1) >0.7 mum, (2) 0.4-0.7 mum and (3) 0.2-0.4 mum and the filtered water phase. The concentrations of chlorophenols (CP), chlorinated phenoxy phenols (PCPP), chlorinated diphenyl ethers (PCDE), chlorinated dibenzofurans (PCDF) and chlorinated dibenzo-p-dioxins (PCDD) were determined in each fraction. The colloids were characterised regarding the chemical composition using X-ray photoelectron spectroscopy (XPS). RESULTS: Chlorophenols were mostly found in the water fraction and PCDD/Fs were found almost exclusively in the particulate fractions. For example, the filtered water phase contained 2,100 mug l(-1) and 0.72 ng l(-1) for CPs and PCDD/Fs, respectively, and the particulate fractions contained 27 mug l(-1) and 32 ng l(-1) for CPs and PCDD/Fs, respectively. XPS evaluation of the particulate phases showed no correlation between the surface chemistry of the particle properties and the distribution of chlorinated compounds. DISCUSSION: The results suggest that groundwater transport of CPs, PCPPs, PCDEs and PCDD/Fs may occur from contaminated sawmill sites and that the colloid-facilitated transport, especially of PCDD/Fs, is substantial. The results correlated well with previous studies of compounds sorbed to dissolved organic carbon, which indicate that dissolved and colloidal organic carbon facilitated the transport of PCDEs, PCDFs and PCDDs particularly. CONCLUSIONS: Several classes of chlorinated compounds were readily detected in the groundwater samples. Due to the differences in their physicochemical properties, CPs, PCPPs, PCDEs and PCDD/Fs vary in their partitioning between colloidal fractions and the filtered groundwater. The proportion of the bound fraction increased with an increasing hydrophobicity of the chlorinated compounds. The groundwater transport of colloid-associated pollutants from the site may be significant. RECOMMENDATIONS AND PERSPECTIVES: The results imply that colloidal particles <0.7 mum are freely mobile in groundwater from this site. The groundwater transport of colloid-associated pollutants may be significant. However, the extent of the problem is not yet known and, thus, further research is needed to evaluate the impact of colloidal transport of hydrophobic organic contaminants. In Sweden alone, 400 to 500 sawmill sites are estimated to be contaminated with PCDD/Fs as a result of the former use of CP-based wood preservatives. The widespread use of CP mixtures for a variety of applications, including wood preservation, indicates that potential colloidal transport will be an issue of concern in many countries.     

Characterization of the toxic effects of cadmium and 3.5-dichlorophenol on nitrifying activity and mortality in biologically activated sludge systems—effect of low temperature

Background, aims, and scope  Sometimes, urban wastewaters convey a more or less significant part of toxic products from industries or the craft industry. Nitrifying activity can be affected by these substances, implying higher ammonia concentrations in the outlet effluent and contributing to toxicity for the aquatic environment. Moreover, the more stringently treated wastewater standards now require a reliable treatment for nitrogen. One of the key issues is the identification of the inhibition behavior of nitrifying bacteria facing a toxic substance. This new understanding could then finally be integrated into models in order to represent and to optimize wastewater treatment plants (WWTP) operation in cases involving ‘toxic scenarios’. Materials and methods  The toxic substances studied in this work, cadmium and 3.5-dichlorophenol (3.5-DCP), are representative of chemical substances commonly found in municipal sewage and industrial effluents and symbolize two different contaminant groups. The effects of Cd and 3.5-DCP on nitrification kinetics have been investigated using respirometry techniques. Results  IC50 values determination gives concentrations of 3.1 mg/L for 3.5-DCP and 45.8 mg/L for Cd at 21 ± 1°C. The variation to low temperature seems to have no real effect on IC50 for DCP, but induces a decrease of cadmium IC50 to 27.5 mg/L at 14°C. Finally, specific respirometric tests have been carried out in order to determine the potential effect of these toxic substances on the nitrifying decay rate b _a . No significant effect has been noticed for Cd, whereas the presence of 3.5-DCP (at IC50 concentration) induced a dramatic increase of b _a at 20°C. The same behavior has been confirmed by experiments performed in winter periods with a sludge temperature around 12°C. Discussion  The target substances have different modes of action on activity and mortality, notably due to the abilities of the contaminant to be precipitated, accumulated, or even to be progressively degraded. Studies realized at low temperature confirmed this assumption, and put in evidence the effect of temperature on toxic substances capable of being biosorbed. However, the change in the sludge sample characteristics can be pointed out as a problem in the investigation of the temperature effect on nitrification inhibition, as biosorption, bioaccumulation, and predation are directly linked to the sludge characteristics (VSS concentration, temperature) and the plant operating conditions (loading rates, sludge age, etc.). Conclusions  This work brings new understandings concerning the action mode of these specific contaminants on nitrifying bacteria and, in particular, on the role of temperature. The experiments lead to the determination of the IC50 values for both toxic substances on biological nitrification. The inhibition mechanisms of Cd and 3.5-DCP on nitrifying activity have been simply represented by a non-competitive inhibition model. Recommendations and perspectives  Other experiments carried out in a continuous lab-scale pilot plant should be done with a proper control of the operating conditions and of the sludge characteristics in order to better understand the mechanisms of nitrification inhibition for each contaminant. Finally, these first results show that toxic substances can have an effect on the growth rate but also on the decay rate, depending on the characteristics of the toxic substance and the sludge. This eventual double effect would imply different strategies of WWTP operation according to the behavior of the contaminant on the bacteria.     

Levels of perfluorochemicals in water samples from Catalonia,Spain: is drinking water a significant contribution to human exposure?

Background, aim, and scope  In recent years, due to a high persistence, biomagnification in food webs, presence in remote regions, and potential toxicity, perfluorochemicals (PFCs) have generated a considerable interest. The present study was aimed to determine the levels of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and other PFCs in drinking water (tap and bottled) and river water samples from Tarragona Province (Catalonia, Spain). Materials and methods  Municipal drinking (tap) water samples were collected from the four most populated towns in the Tarragona Province, whereas samples of bottled waters were purchased from supermarkets. River water samples were collected from the Ebro (two samples), Cortiella, and Francolí Rivers. After pretreatment, PFC analyses were performed by HPLC-MS. Quantification was done using the internal standard method, with recoveries between 68% and 118%. Results  In tap water, PFOS and PFOA levels ranged between 0.39 and 0.87 ng/L (0.78 and 1.74 pmol/L) and between 0.32 and 6.28 ng/L (0.77 and 15.2 pmol/L), respectively. PFHpA, PFHxS, and PFNA were also other detected PFCs. PFC levels were notably lower in bottled water, where PFOS could not be detected in any sample. Moreover, PFHpA, PFHxS, PFOA, PFNA, PFOS, PFOSA, and PFDA could be detected in the river water samples. PFOS and PFOA concentrations were between <0.24 and 5.88 ng/L (<0.48 and 11.8 pmol/L) and between <0.22 and 24.9 ng/L (<0.53 and 60.1 pmol/L), respectively. Discussion  Assuming a human water consumption of 2 L per day, the daily intake of PFOS and PFOA by the population of the area under evaluation was calculated (0.78–1.74 and 12.6 ng, respectively). It was found that drinking water might be a source of exposure to PFCs as important as the dietary intake of these pollutants. Conclusions  The contribution of drinking water (tap and bottled) to the human daily intake of various PFCs has been compared for the first time with data from dietary intake of these PFCs. It was noted that in certain cases, drinking water can be a source of exposure to PFCs as important as the dietary intake of these pollutants although the current concentrations were similar or lower than those reported in the literature for surface water samples from a number of regions and countries. Recommendations and perspectives  Further studies should be carried out in order to increase the knowledge of the role of drinking water in human exposure to PFCs.     

Biological effect monitoring in dab (<Emphasis Type="Italic">Limanda limanda</Emphasis>) using gene transcript of CYP1A1 or EROD—a comparison

BACKGROUND, AIM, AND SCOPE: Gene expression analyses with real-time (RT)-polymerase chain reaction (PCR) gains importance in marine monitoring. This new technique has to be compared to the classical approaches like the well known biomarker ethoxyresorufin-O-deethylase (EROD) to test their suitability for monitoring programmes. The goal of the present study is to compare EROD activity and CYP1A1 mRNA expression in the important monitoring fish species dab (Limanda limanda) and to answer the question of whether these parameters reflect the polycyclic aromatic hydrocarbon (PAH) contamination of the fish. Further on, glyceraldehyd-3-phosphate dehydrogenase (GAPDH) was investigated as a potential housekeeping gene. MATERIALS AND METHODS: Female dab were caught in the summer of 2004 in the North Sea and in the Baltic. EROD activity was determined in liver samples by a kinetic fluorimetric assay according to a standard protocol. The gene expression of CYP1A (cytochrome P450 1A) and GAPDH were determined by means of RT-PCR. Results were compared to gonado somatic index and to the concentration of PAH metabolite 1OHPyr (1-hydroxypyrene) analysed in the bile fluids of the fish, respectively. RESULTS: Dab from all stations showed a considerable individual variation in the levels of both CYP1A mRNA and EROD. Highest mean values for CYP1A mRNA and EROD were detected in the northern part of the sampling area. In contrast, the PAH metabolite 1OHPyr was found at the highest concentration in fish caught near the German coast. CYP1A mRNA and EROD showed only a minor but significant correlation (r = 0.32, p < 0.05, n = 123). 1OHPyr in bile correlated significantly (p < 0.05) with the amount of GAPDH mRNA content in the liver. DISCUSSION: The significant but low correlation of CYP1A mRNA and EROD activity on an individual basis illustrates that these two parameters are apparently not closely linked. However, maximum EROD values correspond with maximum CYP1A mRNA concentrations when station means are regarded. Because EROD and CYP1A mRNA in dab follow different physiological principles, their application will lead to related but not identical monitoring results. This should be taken into account when future marine monitoring programmes are designed. The results also indicate that PAH are not the crucial factor for CYP1A and EROD levels in dab from the off-shore areas in the North Sea. This is remarkable because the PAH metabolism is known to be CYP1A-dependent and the widely used biomarker EROD has been recommended for monitoring PAH-related effects in fish from the North Sea. Due to a correlation between GAPDH and 1OHPyr, GAPDH was not suitable as housekeeping gene for dab. CONCLUSIONS: Neither the results from EROD nor from CYP1A1 mRNA measurements in dab reflected their exposure to PAH as measured by the PAH metabolite 1OHPyr. Thus, the question arises of whether EROD or CYP1A mRNA is a suitable biomarker at all to indicate PAH exposure in dab from the open North Sea. RECOMMENDATIONS AND PERSPECTIVES: For future biological effect monitoring, it is advisable to measure more and predominately independent parameters by RT-PCR and to incorporate more components of the detoxification system.