A tiered procedure for assessing the formation of biotransformation products of pharmaceuticals and biocides during activated sludge treatment

Upon partial degradation of polar organic micropollutants during activated sludge treatment, transformation products (TPs) may be formed that enter the aquatic environment in the treated effluent. However, TPs are rarely considered in prospective environmental risk assessments of wastewater-relevant compound classes such as pharmaceuticals and biocides. Here, we suggest and evaluate a tiered procedure, which includes a fast initial screening step based on high resolution tandem mass spectrometry (HR-MS/MS) and a subsequent confirmatory quantitative analysis, that should facilitate consideration of TPs formed during activated sludge treatment in the exposure assessment of micropollutants. At the first tier, potential biotransformation product structures of seven pharmaceuticals (atenolol, bezafibrate, ketoprofen, metoprolol, ranitidine, valsartan, and venlafaxine) and one biocide (carbendazim) were assembled using computer-based biotransformation pathway prediction and known human metabolites. These target structures were screened for in sludge-seeded batch reactors using HR-MS/MS. The 12 TPs found to form in the batch experiments were then searched for in the effluents of two full-scale, municipal wastewater treatment plants (WWTPs) to confirm the environmental representativeness of this first tier. At the second tier, experiments with the same sludge-seeded batch reactors were carried out to acquire kinetic data for major TPs that were then used as input parameters into a cascaded steady-state completely-stirred tank reactor (CSTR) model for predicting TP effluent concentrations. Predicted effluent concentrations of four parent compounds and their three major TPs were corroborated by comparison to 3-day average influent and secondary effluent mass flows from one municipal WWTP. CSTR model-predicted secondary effluent mass flows agreed within a factor of two with measured mass flows and confidence intervals of predicted and measured mass flows overlapped in all cases. The observed agreement suggests that the combination of batch-determined transformation kinetics with a simple WWTP model may be suitable for estimating aquatic exposure to TPs formed during activated sludge treatment. Overall, we recommend the tiered procedure as a realistic and cost-effective approach to include consideration of TPs of wastewater-relevant compounds into exposure assessment in the context of prospective chemical risk assessment.     

Monitoring the impact of dissolved oxygen and nitrite on anoxic biofilm in continuous denitrification process

An anoxic biofilm involved in continuous denitrificationprocess was monitored to investigate the effect of differentconcentrations of influent dissolved oxygen (DO) or nitrite onthe biofilm. Microelectrode measurements evidenced nitrateremoval activity of biofilm. When different concentrations ofDO were applied to the reactor, generally decreasedconcentrations of DO were observed as bed depth increased fromthe bottom of the reactor. Greatest decrease of the DO wasobserved in the lower 20% of the bed depth. Nitrate removalefficiency was inversely proportional to influent DOconcentrations (8.3-11.9 DO mg L^-1) or nitrite loadingrates (0-5.5 N-NO₂ ^- kg m^-3 day^-1) employed in this study. Nitrite loading rates to achieve morethan 90% of nitrate removal efficiency were 1.46 N-NO₂ ^-kg m^-3 day^-1 or less at pH 7.5 and 0.34 N-NO₂ ^- kg m^-3 day^-1 or less at pH 6.8. Nitrate removal efficiency was 63% or more within the lower 20% of the bed depth at the nitrite loading rates that allowed more than 90% of nitrate removal efficiency of the reactor. The results of this study provide first quantitative data that nitrate removalperformance of an anoxic biofilm is inhibited by DO or nitrite,reported to be a limiting factor in the suspended biologicaldenitrification process.     

Monitoring of copper,arsenic and antimony levels in agricultural soils impacted and non-impacted by mining activities,from three regions in Chile

This paper reports a comparative study of the concentration of three important environmental elements that are often found together in mineral deposits and then associated with mining activities; copper, arsenic and antimony. These elements were determined in 26 different agricultural soils from regions I, II and V in Chile, zones where the most important and biggest copper industries of this country are located. As background levels of these elements in soils have not been well established, in this study, both, impacted and non-impacted agricultural soils from different regions were considered. The relationships between the concentrations of these elements in soils were also examined. The concentration ranges for copper, arsenic and antimony were 11-530; 2.7-202 and 0.42-11 mg kg(-1) respectively. The copper concentrations in non-polluted soils from the north and central zone of Chile were similar. However, three sites from the north region have copper concentration as higher as 100 mg kg(-1), values that exceed the critical concentration for copper in soils. The concentration of arsenic and antimony in the north soils were higher than in non-impacted ones and, in the case of arsenic, greatly exceeded the world average concentration reported for this element in soils. The highest arsenic and antimony concentrations were found in Calama and Quillagua soils, two different sites in the Loa valley. The arsenic/antimony concentration ratio was higher in Quillagua soil. The high concentrations of three elements determined in impacted soils from region V (Puchuncaví and Catemu valleys) clearly shows the impact produced in this zone by the industrial and mining activities developed in their proximities. At Puchuncaví valley a clear decrease was observed in copper, arsenic and antimony concentrations in soils on the function of the distance from the industrial complex "Las Ventanas", and all concentrations exceeded the reported critical values for this matrix. Instead at Catemu valley, only the copper concentration was higher than this value. Statistically significant correlation was found for Cu-Sb in all soils; more significant Cu-As, Cu-Sb and Sb-As correlations were evaluated for soils from Puchuncaví and Catemu valleys, corroborating that high concentrations of copper, arsenic and antimony in these soils coming from the same pollution sources, the copper industry and the thermoelectric power plant.     

Monitoring of glyphosate and AMPA in soil samples from two olive cultivation areas in Greece: aspects related to spray operators activities

The persistence of glyphosate and its primary metabolite AMPA (aminomethylphosphonic acid) was monitored in two areas in Southern Greece (Peza, Crete and Chora Trifilias, Peloponnese) with a known history of glyphosate use, and the levels of residues were linked to spray operators’ activities in the respective areas. A total of 170 samples were collected and analysed from both areas during a 3-year monitoring study. A new method (Impact Assessment Procedure - IAP) designed to assess potential impacts to the environment caused by growers’ activities, was utilised in the explanation of the results. The level of residues was compared to the predicted environmental concentrations in soil. The ratio of the measured concentrations to the predicted environmental concentrations (MCs/PECs) was >?1 in Chora the first 2 years of sampling and <?1 in the third year, whilst the MCs/PECs ratio was <?1 in Peza, throughout the whole monitoring period. The compliance to the instructions for best handling practices, which operators received during the monitoring period, was reflected in the amount of residues and the MCs/PECs ratio in the second and especially the third sampling year. Differences in the level of residues between areas as well as sampling sites of the same area were identified. AMPA persisted longer than the parent compound glyphosate in both areas.     

Monitoring and validating the temporal dynamics of interday streamflow from two upland head micro-watersheds with different vegetative conditions during dry periods of the growing season in the Bohemian Massif,Czech Republic

At present, dynamic land use, climate change, and growing needs for fresh water are increasing the demand on the ecosystem effects of forest vegetation. Mountainous areas are at the forefront of scientific interest in European forest ecology and forest hydrology. Although uplands cover a significant area of the Czech Republic and other countries and are often covered with forest formations, they do not receive an appropriate amount of attention. Therefore, two experimental upland head micro-watersheds in the Bohemian Massif were selected for study because they display similar natural conditions, but different vegetative conditions (forest versus meadow). During the 2011 growing season, short-term streamflow measurements were carried out at the discharge profiles of both catchments and were evaluated in relation to climatic data (rainfall and temperature). The basic premise was that the streamflow in a forested catchment must exhibit different temporal dynamics compared to that in treeless areas and that these differences can be attributed to the effects of woody vegetation. These conclusions were drawn from measurements performed during dry periods lasting several days. A decreasing streamflow trend during the day part of the day (0900–1900 hours) was observed in both localities. The decrease reached approx. 44 % of the initial morning streamflow (0.24 dm³ s^?1 day^?1) in the treeless catchment and approx. 20 % (0.19 dm³ s^?1 day^?1) in the forested catchment. At night (1900–0900 hours), the streamflow in the forested catchment increased back to its initial level, whereas the streamflow in the treeless catchment stagnated or slowly decreased. We attribute these differences to the ecosystem effects of woody vegetation and its capacity to control water loss during the day. This type of vegetation can also function as a water source for the hydrographic network during the night.     

Effects of transgenic Bt cotton on soil fertility and biology under field conditions in subtropical inceptisol

Although there is large-scale adoption of Bt cotton by the farmers because of immediate financial gain, there is concern that Bt crops release Bt toxins into the soil environment which reduces soil chemical and biological activities. However, the majorities of such studies were mainly performed under pot experiments, relatively little research has examined the direct and indirect effects of associated cover crop of peanut with fertilization by combined application of organic and inorganic sources of nitrogen under field conditions. We compared soil chemical and biological parameters of Bt cotton with pure crop of peanut to arrive on a valid conclusion. Significantly higher dehydrogenase enzyme activity and KMnO₄-N content of soil were observed in Bt cotton with cover crop of peanut over pure Bt cotton followed by pure peanut at all the crop growth stages. However, higher microbial population was maintained by pure peanut over intercropped Bt cotton, but these differences were related to the presence of high amount of KMnO₄-N content of soil. By growing cover crop of peanut between Bt cotton rows, bacteria, fungi, and actinomycetes population increased by 60%, 14%, and 10%, respectively, over Bt cotton alone. Bt cotton fertilized by combined application of urea and farm yard manure (FYM) maintained higher dehydrogenase enzyme activity, KMnO₄-N content of soil and microbial population over urea alone. Significant positive correlations were observed for dry matter accumulation, dehydrogenase enzyme activity, KMnO₄-N content, and microbial population of soil of Bt cotton, which indicates no harmful effects of Bt cotton on soil biological parameters and associated cover crop. Our results suggest that inclusion of cover crop of peanut and FYM in Bt cotton enhanced soil chemical and biological parameters which can mask any negative effect of the Bt toxin on microbial activity and thus on enzymatic activities.     

Release of arsenic (As) and lead (Pb) from quicklime-sulfate stabilized/solidified soils under diffusion-controlled conditions

A quicklime-sulfate-based stabilization/ solidification (S/S) process for arsenic (As) and lead (Pb) immobilization was evaluated under “semi-dynamic” leaching conditions. In order to simulate aggressive leaching conditions the semi-dynamic leaching tests was modified by using 0.014 N of acetic solution instead of distilled water. Kaolinite-sand and montmorillonite-sand soil samples were artificially contaminated with As and Pb, compacted and cured for 28 days. The semi-dynamic leaching tests were then conducted for 90 days. The effectiveness of the S/S treatment was evaluated by assessing the cumulative release of As and Pb as well as by determining the diffusion coefficients (D _eff) and leachability indices (LX). The release of As and Pb was greatly reduced by quicklime-sulfate treatment as compared to untreated samples. Moreover, the quicklime-sulfate treatment was more effective than the quicklime-only treatment in reducing both As and Pb release. The controlling leaching mechanisms were determined using a diffusion theory model. Upon S/S treatment, As and Pb release was diffusion controlled. The LX of all the treated samples were greater than nine, suggesting that S/S treated samples were suitable for “controlled utilization”.     

Degradation of three fungicides following application on strawberry and a risk assessment of their toxicity under greenhouse conditions

The health risk to humans of pesticide application on minor crops, such as strawberry, requires quantification. Here, the dissipation and residual levels of three fungicides (pyraclostrobin, myclobutanil, and difenoconazole) were studied for strawberry under greenhouse conditions using high-performance liquid chromatography (HPLC)-tandem mass spectrometry after Quick, Easy, Cheap, Effective, Rugged, and Safe extraction. This method was validated using blank samples, with all mean recoveries of these three fungicides exceeding 80 %. The residues of all three fungicides dissipated following first-order kinetics. The half-lives of pyraclostrobin, myclobutanil, and difenoconazole were 1.69, 3.30, and 3.65 days following one time application and 1.73, 5.78, and 6.30 days following two times applications, respectively. Fungicide residue was determined by comparing the estimated daily intake of the three fungicides against the acceptable daily intake. The results indicate that the potential health risk of the three fungicides was not significant in strawberry when following good agricultural practices (GAP) under greenhouse conditions.     

Effects of anthropogenic nitrogen deposition on soil nitrogen mineralization and immobilization in grassland soil under semiarid climatic conditions

Earlier studies by the authors on English soils under grassland strongly supported their hypothesis that soil/plant systems have naturally evolved to conserve nitrogen (N) by having a close match between the dynamics of mineral-N production in soils and the dynamics of plant N requirements. Thus, maximum mineral-N production in soils occurred in spring when plant N requirements were greatest and were very low in mid to late summer. Low temperature and a high C:N ratio of senescing material helped to conserve N in winter, but mobile N was associated with pollution inputs. We test the hypothesis that under the much more arid conditions of Pakistan, soil/plant systems naturally have evolved to conserve mineral-N, especially over the very dry and cooler months between October and February. When soils from a grassland site were incubated at ambient temperatures after removal of plant roots and exclusion of atmospheric N inputs, there was consistent evidence of immobilization of nitrate and immobilization and possibly volatilization of ammonia/ammonium. In the wetter months of July and August, the soil at 0–10 cm depth showed no evidence of significant ammonium-N production in July and only small ammonium production at 10–20 cm depth in August, but was associated with significant nitrate-N immobilization in August. Nitrate leaching only appeared likely towards the end of the rainy season in September. The results strongly suggest that, under grass, the retention of atmospheric N inputs over the long dry periods is regulating the pools of available N in the soils, rather than the N produced by mineralization of soil organic matter.     

Impact of elevated O3 on visible foliar symptom, growth and biomass of Cinnamomum camphora seedlings under different nitrogen loads

The effects of elevated ozone (O(3)) and enhanced nitrogen (N) on the growth and biomass of Cinnamomum camphora, a subtropical evergreen broad-leaved tree species, were investigated. The seedlings, supplied with N (NH(4)NO(3) solution) at 0, 30 and 60 kg ha(-1) year(-1) (simplified as N0, N30, N60, respectively), were exposed to ambient (AA) or elevated O(3) (AA + 60 nmol mol(-1) and AA + 120 nmol mol(-1), designated as AA + 60 and AA + 120, respectively) for the 2009 and 2010 growing seasons. Symptomatic leaf percentages were significantly increased with O(3) concentration. AA + 120 significantly decreased the mean leaf size and chlorophyll content of both 2009- and 2010-emerged leaves, inhibited the growth of stem height and basal diameter, and reduced biomass accumulation of all plant parts except for leaves. By comparison, only the chlorophyll content of 2009-emerged leaves and root dry weight were significantly reduced under AA + 60. Specific leaf area, total leaf area and foliar biomass were not affected even at a higher O(3) level. On the other hand, N loads, especially N60, exerted significantly positive effects on all variables except mean leaf size and shoot/root ratio. No significant interactions between O(3) and N were detected, suggesting that the N supply at ≤60 kg ha(-1) year(-1) did not significantly modify the response of C. camphora to O(3) in terms of seedling growth and biomass accumulation.     

Comparison of Nitrate Levels in Raw Water and Finished Water from Historical Monitoring Data on Iowa Municipal Drinking Water Supplies

Nitrate contamination of water sources is a concern where large amounts of nitrogen fertilizers are regularly applied to soils. Ingested nitrate from dietary sources and drinking water can be converted to nitrite and ultimately to N-nitroso compounds, many of which are known carcinogens. Epidemiologic studies of drinking water nitrate and cancer report mixed findings; a criticism is the use of nitrate concentrations from retrospective drinking water data to assign exposure levels. Residential point-of-use nitrate data are scarce; gaps in historical data for municipal supply finished water hamper exposure classification efforts. We used generalized linear regression models to estimate and compare historical raw water and finished water nitrate levels (1960s--1990s) in single source Iowa municipal supplies to determine whether raw water monitoring data could supplement finished water data to improve exposure assessment. Comparison of raw water and finished water samples (same sampling date) showed a significant difference in nitrate levels in municipalities using rivers; municipalities using other surface water or alluvial groundwater had no difference in nitrate levels. A regional aggregation of alluvial groundwater municipalities was constructed based on results from a previous study showing regional differences in nitrate contamination of private wells; results from this analysis were mixed, dependent upon region and decade. These analyses demonstrate using historical raw water nitrate monitoring data to supplement finished water data for exposure assessment is appropriate for individual Iowa municipal supplies using alluvial groundwater, lakes or reservoirs. Using alluvial raw water data on a regional basis is dependent on region and decade.     

Impact of emission from oil shale fueled power plants on the growth and foliar elemental concentrations of Scots pine in Estonia

To study the impact of air pollution on the growth and elemental composition of conifers, 5 sample plots wereestablished at different distances and directions from theEstonian Power Plant (Northeast Estonia) in 1999–2000. Theselected stands were 75–80(85)-yr-old parts (0.05 ha) of(Oxalis)-Myrtillus site type forest of 0.7–0.8density. The soils of all sample plots were Gleyic Podzols(Lkg) on sands. The several times higher Ca concentration inthe humus horizon of the sample plot NE from the Estonian PPis caused by the prevailing westerly and southerly winds whichcarry more pollutants NE from the power plant than to SSW. Toascertain the effect of power plants on the growth of Scotspine (Pinus sylvestris L.), the length growth of theneedles and shoots formed in 1997–2000, dry weight of 100needles, and density of needles on the shoots were measured.As compared to the control, the strongest inhibition of growthwas revealed in the sample plots situated 22 km north-east and17 km south-west from the Estonian Power Plant. As compared tocontrol, the needles of trees growing on sample plots closerto the power plant showed higher contents of Ca, S and Zn. Thecontent of Mg in needles increased with distance from thepollution source. Current year needles had higher contents ofCu and Zn than older needles. Today the amounts of fly ashemitted from Narva power plants are fallen. Long-term fly ashemission has caused changes in the measurements ofmorphological parameters and chemical composition of needles.     

Effect of nitrogen, potassium and humic acid on 134 Cs transfer factors to wheat from tropical soils in Neubauer growth units

A Neubauer plantlet experiment was carried out using Inceptisol (Typic Haplustept) and Vertisol (Typic Chromustert) soils contaminated with 134Cs at 74 kBq kg(-1) soil to study the transfer factor to wheat crop (Triticum aestivum) as influenced by four levels of humic acid (100, 200, 300, 400 mg HA kg(-1) soil), potassium and NH4-N (36.4, 54.5, 72.7 and 90.9 mg K or NH4 kg(-1) soil) under tropical climate. The biomass yield and K uptake by wheat were significantly improved in Vertisol with NH4-N and K application. The potassium application significantly increased the potassium concentration in wheat plants. The increase in the levels of each of the treatments dramatically improved the yield, K content and K uptake parameters, irrespective of the soils. The 134Cs transfer factors, irrespective of the treatments were observed to be higher in Vertisols as compared to Inceptisols. Among the treatments, the effect of HA was significantly greater than that of K and NH4-N application in Inceptisol, however, in Vertisols both HA and NH4-N were observed to be superior as compared to K application. With each increment in the levels of the treatments, a significantly lowered TF value was found, higher in Inceptisols (56.3%) than Vertisols (48.5%). Comparison of treatments indicates that in general higher potassium concentration in plant drastically lowered radiocesium transfer to wheat. Neubauer plant culture study, a rapid laboratory experimental model based on simple soil-plant system was quite clearly brought out the potential effectiveness of N, K and HA on soil-to-wheat transfer of radiocesium. Such screening technique needs to be extended to cover wider crop species, different climatic conditions and factors governing/modifying the mobility of radiocesium in soil and its absorption by crop plants.     

Comparative studies on accumulation of Cr from metal solution and tannery effluent under repeated metal exposure by aquatic plants: its toxic effects

The present study demonstrates comparison of Cr accumulatingpotential by the plants of Najas indica Cham. (submerged),Vallisneria spiralis L. (rooted submerged) and Alternanthera sessilis R. Br. (rooted emergent) under repeatedmetal exposure and its effect on chlorophyll and protein concentrations. These plants were treated with different concentrations of Cr under repeated exposure in controlled laboratory conditions to assess the maximum metal accumulationpotential. The plants of V. spiralis accumulated significantly high amount of Cr under laboratory conditions incomparison to N. indica and A. sessilis. The maximumaccumulation of 1378, 458 and 201 g g^-1 dw Cr was found in the leaves of V. spiralis, N. indica and A. sessilis, respectively at 8 mg L^-1 after 9 day of Cr exposure. These plants have shown a decrease in chlorophyll andprotein concentrations with increase in Cr concentrations. In view of high accumulation of Cr in V. spiralis, the plantswere treated with different concentrations of tannery effluent collected from Common Effluent Treatment Plant, Unnao (UP). Theplants of V. spiralis treated with 100% tannery wastewatershowed the maximum accumulation (57.5 g g^-1 dw) of Cr in the roots after 10 days of exposure. The plants were foundeffective in removing Cr from solution and tannery effluent.     

Artificial soils from alluvial tin mining wastes in Malaysia--a study of soil chemistry following experimental treatments and the impact of mycorrhizal treatment on growth and foliar chemistry

For decades Malaysia was the world's largest producer of Sn, but now the vast open cast mining operations have left a legacy of some 100,000 ha of what is effectively wasteland, covered with a mosaic of tailings and lagoons. Few plants naturally recolonise these areas. The demand for such land for both urban expansion and agricultural use has presented an urgent need for better characterisation. This study reports on the formation of artificial soils from alluvial Sn mining waste with a focus on the effects of experimental treatments on soil chemistry. Soil organic matter, clay, and pH were manipulated in a controlled environment. Adding both clay tailings and peat enhanced the cation exchange capacity of sand tailings but also reduced the pH. The addition of peat reduced the extractable levels of some elements but increased the availability of Ca and Mg, thus proving beneficial. The use of clay tailings increased the levels of macro and micronutrients but also released Al, As, La, Pb and U. Additionally, the effects of soil mix and mycorrhizal treatments on growth and foliar chemistry were studied. Two plant species were selected: Panicum milicaeum and Pueraria phaseoloides. Different growth patterns were observed with respect to the additions of peat and clay. The results for mycorrhizal treatment (live inoculum or sterile carrier medium) are more complex, but both resulted in improved growth. The use of mycorrhizal fungi could greatly enhance rehabilitation efforts on sand tailings.