Monitoring of the ecotoxicological hazard potential by polar organic micropollutants in sewage treatment plants and surface waters using a mode-of-action based test battery

We propose and evaluate a mode-of-action based test battery of low-complexity and in-vitro bioassays that can be used as a routine monitoring tool for sewage treatment efficiency and water quality assessment. The test battery comprises five bioassays covering five different modes of toxic action. The bioluminescence inhibition test with Vibrio fischeri and a growth rate inhibition test with the green algae Pseudokirchneriella subcapitata are measures of non-specific integrative effects. A second endpoint in the algae test, the specific inhibition of the efficiency of photosynthesis, gives an account of the presence of herbicides. An enzymatic assay covers an important aspect of insecticidal activity, the inhibition of the acetylcholine esterase activity. Estrogenic effects are assessed with the yeast estrogen screen (YES) and genotoxicity with the umuC test. Three field studies, each lasting six to seven consecutive days, were undertaken at a sewage treatment plant (STP) in Switzerland. Samples were collected in summer and late autumn, under dry and rainy conditions. None of the bioassays gave positive results with raw water in whole effluent toxicity testing. Therefore, water samples from various sites during wastewater treatment and from surface water were enriched with solid-phase extraction. The focus was on non-volatile compounds of average to moderate hydrophobicity, a range that includes most pesticides, biocides and pharmaceuticals. Various polar solid phases were evaluated for their extraction efficiency, disturbance by matrix components and overall performance. We finally selected a mixture of a polymeric sorbent and a C18-sorbent, Lichrolut EN and RP-18 or, alternatively, Empore SDB-RPS disks. All bioassays gave clear and robust responses with the SPE extracts. With the bioassay data the treatment efficiency of the STP can be assessed with respect to different modes of toxic action and accordingly different groups of micropollutants. Furthermore, the data allowed for a comparison between the effluent and the receiving river. In all bioassays the primary effluent had a strong effect and this effect was reduced after passing the STP. Treatment efficiency was high (typically over 90%) but varied from bioassay to bioassay, which is expected because each bioassay detects different types of micropollutants and therefore we cannot expect a common answer.     

Preliminary assessment of polybrominated diphenyl ethers (PBDEs) in the Scottish aquatic environment, including the Firth of Clyde

This paper presents preliminary data on polybrominated diphenyl ethers (PBDEs) in the Scottish aquatic environment. Sediment and biota (fish liver, fish muscle and mussels) from a number of locations around Scotland were analysed for PBDEs with samples being from both remote and from potentially contaminated areas such as the former sewage sludge dump site at Garroch Head in the Clyde. PBDEs were measured in both cultivated, rope grown mussels and wild mussels collected from 5 sites around Scotland in 2006. Total PBDE concentrations (sum of tri- to hepta-BDEs) ranged from 相似文献   

Effect of nitrogen fertilizer application on growing season soil carbon dioxide emission in a corn-soybean rotation

Nitrogen application can have a significant effect on soil carbon (C) pools, plant biomass production, and microbial biomass C processing. The focus of this study was to investigate the short-term effect of N fertilization on soil CO(2) emission and microbial biomass C. The study was conducted from 2001 to 2003 at four field sites in Iowa representing major soil associations and with a corn (Zea mays L.)-soybean (Glycine max L. Merr.) rotation. The experimental design was a randomized complete block with four replications of four N rates (0, 90, 180, and 225 kg ha(-1)). In the corn year, season-long cumulative soil CO(2) emission was greatest with the zero N application. There was no effect of N applied in the prior year on CO(2) emission in the soybean year, except at one of three sites, where greater applied N decreased CO(2) emission. Soil microbial biomass C (MBC) and net mineralization in soil collected during the corn year was not significantly increased with increase in N rate in two out of three sites. At all sites, soil CO(2) emission from aerobically incubated soil showed a more consistent declining trend with increase in N rate than found in the field. Nitrogen fertilization of corn reduced the soil CO(2) emission rate and seasonal cumulative loss in two out of three sites, and increased MBC at only one site with the highest N rate. Nitrogen application resulted in a reduction of both emission rate and season-long cumulative emission of CO(2)-C from soil.     

Atrazine sorption and fate in a Ultisol from humid tropical Brazil

This study combined laboratory based microcosm systems as well as field experiments to evaluate the mobility of atrazine on a Ultisol under humid tropical conditions in Brazil. Results from sorption experiments fit to the Freundlich isotherm model [K(f) 0.99 mg kg(-1)/(mg l(-1))(1/n)], and indicate a low sorption capacity for atrazine in this soil and consequently large potential for movement by leaching and runoff. Microcosm systems using (14)C-atrazine to trace the fate of the applied herbicide, showed that 0.33% of the atrazine was volatilized, 0.25% mineralized and 6.89% was recorded in the leachate. After 60 d in the microcosms, 75% of the (14)C remained in the upper 5 cm soil layer indicating atrazine or its metabolites remained close to the soil surface. In field experiments, after 60 d, only 5% of the atrazine applied was recovered in the upper soil layers. In the field experiments atrazine was detected at a depth of 50 cm indicating leaching. Simulating tropical rain in field experiments resulted in 2.1% loss of atrazine in runoff of which 0.5% was adsorbed onto transported soil particles and 1.6% was in solution. Atrazine runoff was greatest two days after herbicide application and decreased 10 fold after 15 d. The use of atrazine on Ultisols, in the humid tropics, constitutes a threat to water quality, causing surface water and ground water pollution.     

Photodegradation of organophosphorus insecticides - investigations of products and their toxicity using gas chromatography-mass spectrometry and AChE-thermal lens spectrometric bioassay

Four organophosphorus compounds: azinphos-methyl, chlorpyrifos, malathion and malaoxon in aqueous solution were degraded by using a 125 W xenon parabolic lamp. Gas chromatography-mass spectrometry (GC-MS) was used to monitor the disappearance of starting compounds and formation of degradation products as a function of time. AChE-thermal lens spectrometric bioassay was employed to assess the toxicity of photoproducts. The photodegradation kinetics can be described by a first-order degradation curve C=C0e(-kt), resulting in the following half lives: 2.5min for azinphos-methyl, 11.6 min for malathion, 13.3 min for chlorpyrifos and 45.5 min for malaoxon, under given experimental conditions. During the photoprocess several intermediates were identified by GC-MS suggesting the pathway of OP degradation. The oxidation of chlorpyrifos results in the formation of chlorpyrifos-oxon as the main identified photoproduct. In case of malathion and azinphos-methyl the corresponding oxon analogues were not detected. The formation of diethyl (dimethoxy-phosphoryl) succinate in traces was observed during photodegradation of malaoxon and malathion. Several other photoproducts including trimethyl phosphate esters, which are known to be AChE inhibitors and 1,2,3-benzotriazin-4(3H)-one as a member of triazine compounds were identified in photodegraded samples of malathion, malaoxon, and azinphos-methyl. Based on this, two main degradation pathways can be proposed, both result of the (P-S-C) bond cleavage taking place at the side of leaving group. The enhanced inhibition of AChE observed with the TLS bioassay during the initial 30 min of photodegradation in case of all four OPs, confirmed the formation of toxic intermediates. With the continuation of irradiation, the AChE inhibition decreased, indicating that the formed toxic compounds were further degraded to AChE non-inhibiting products. The presented results demonstrate the importance of toxicity monitoring during the degradation of OPs in processes of waste water remediation, before releasing it into the environment.     

Soil and vegetation carbon stocks in Brazilian Western Amazonia: relationships and ecological implications for natural landscapes

The relationships between soils attributes, soil carbon stocks and vegetation carbon stocks are poorly know in Amazonia, even at regional scale. In this paper, we used the large and reliable soil database from Western Amazonia obtained from the RADAMBRASIL project and recent estimates of vegetation biomass to investigate some environmental relationships, quantifying C stocks of intact ecosystem in Western Amazonia. The results allowed separating the western Amazonia into 6 sectors, called pedo-zones: Roraima, Rio Negro Basin, Tertiary Plateaux of the Amazon, Javari-Juruá-Purus lowland, Acre Basin and Rondonia uplands. The highest C stock for the whole soil is observed in the Acre and in the Rio Negro sectors. In the former, this is due to the high nutrient status and high clay activity, whereas in the latter, it is attributed to a downward carbon movement attributed to widespread podzolization and arenization, forming spodic horizons. The youthful nature of shallow soils of the Javari-Juruá-Purus lowlands, associated with high Al, results in a high phytomass C/soil C ratio. A similar trend was observed for the shallow soils from the Roraima and Rondonia highlands. A consistent east–west decline in biomass carbon in the Rio Negro Basin sector is associated with increasing rainfall and higher sand amounts. It is related to lesser C protection and greater C loss of sandy soils, subjected to active chemical leaching and widespread podzolization. Also, these soils possess lower cation exchangeable capacity and lower water retention capacity. Zones where deeply weathered Latosols dominate have a overall pattern of high C sequestration, and greater than the shallower soils from the upper Amazon, west of Madeira and Negro rivers. This was attributed to deeper incorporation of carbon in these clayey and highly pedo-bioturbated soils. The results highlight the urgent need for refining soil data at an appropriate scale for C stocks calculations purposes in Amazonia. There is a risk of misinterpreting C stocks in Amazonia when such great pedological variability is not taken into account.     

Pesticide Residues in Bovine Milk from a Predominantly Agricultural State of Haryana, India

One hundred forty seven samples of bovine milk were collected from 14 districts of Haryana, India during December 1998–February 1999 and analysed for the presence of organochlorine pesticide (OCPs) residues. ∑HCH, ∑DDT, ∑endosulfan and aldrin were detected in 100%, 97%, 43% and 12% samples and with mean values of 0.0292, 0.0367, 0.0022 and 0.0036 μg/ml, respectively. Eight percent samples exceeded the maximum residue limit (MRL) of 0.10 mg/kg as recommended by WHO for ∑HCH, 4% samples of 0.05 mg/kg for α-HCH, 5% samples of 0.01 mg/kg for γ-HCH, 26% samples of 0.02 mg/kg for β-HCH as recommended by PFAA and 24% samples of 0.05 mg/kg as recommended by FAO for ∑DDT. Concentrations of β-HCH and p,p′-DDE were more as compared to other isomers and metabolites of HCH and DDT.     

Rapid growth of clones of the red alga Chondrus crispus: applications in assays of toxic substances and in physiological studies

Growth rates of excised apical segments from three Chondrus crispus Stackhouse clones were rapid, reproducible and easily measured using simple equipment. Clonal segments exhibited a high degree of phenotypic stability, with coefficients of variation in growth rates being typically less than 5%. Sensitivity of the assay was demonstrated using 24-h pulses of the toxicants Cu²⁺ (10 to 150 ppb) and the molluscicide Bayluscide (100 to 500 ppb). As a further demonstration of applicability of this assay system, growth rates were measured over two consecutive 24-h photoperiods using a normally pigmented red gametophytic clone and a green colored mutant derived from it. Growth rates were highest in the first hours of the light phase for both clones, with growth of the green mutant being consistently inferior to that of the normally pigmented one. Significant changes were measured with intervals as short as 4 h using only five apical segments for each treatment. The C. crispus assay described is sensitive, relatively rapid, and statistically robust when applied to toxicant testing in seawater and to physiological studies.