Heterogeneous photocatalytic degradation of pesticides using decatungstate intercalated macroporous layered double hydroxides

Decatungstate W₁₀O₃₂ ^4? was efficiently intercalated between the layers of three-dimensionally ordered macroporous Mg₂Al-layered double hydroxide. The structural and textural properties of as-prepared intercalated compound were characterized using different solid-state characterization techniques such as X-ray powder diffraction, FTIR and Raman spectroscopies and electronic microscopy. The photocatalytic properties of immobilized W₁₀O₃₂ ^4? within Mg₂Al structure were investigated using 2-(1-naphthyl) acetamide (NAD) as a model of pesticide. The influence of different parameters such as amount of catalyst, pH and oxygen concentration were investigated. An optimal NAD degradation was obtained for a photocatalyst concentration of 60 mg l^?1. Under our experimental conditions, this heterogeneous photocatalyst induces photodegradation of 60 % of NAD after 17 h of irradiation at 365 nm and at pH 6.6. Interestingly, pesticide photodegradation leads to the mineralization of substrates to H₂O and CO₂ and the photocatalyst can be recycled and reused without any loss of activity over four cycles.     

Effects of light and temperature fluctuations on the growth of Myriophyllum spicatum in toxicity tests—a model-based analysis

Laboratory toxicity tests are a key component of the aquatic risk assessments of chemicals. Toxicity tests with Myriophyllum spicatum are conducted based on working procedures that provide detailed instructions on how to set up the experiment, e.g., which experimental design is necessary to get reproducible and thus comparable results. Approved working procedures are established by analyzing numerous toxicity tests to find a compromise between practical reasons (e.g., acceptable ranges of ambient conditions as they cannot be kept completely constant) and the ability for detecting growth alterations. However, the benefit of each step of a working procedure, e.g., the random repositioning of test beakers, cannot be exactly quantified, although this information might be useful to evaluate working procedures. In this paper, a growth model of M. spicatum was developed and used to assess the impact of temperature and light fluctuations within the standardized setup. It was analyzed how important it is to randomly reassign the location of each plant during laboratory tests to keep differences between the relative growth rates of individual plants low. Moreover, two examples are presented on how modeling can give insight into toxicity testing. Results showed that randomly repositioning of individual plants during an experiment can compensate for fluctuations of light and temperature. A method is presented on how models can be used to improve experimental designs and to quantify their benefits by predicting growth responses.     

Strategies to evaluate biodegradability: application to chlorinated herbicides

The biodegradability of nitrochlorinated (diuron and atrazine) and chlorophenoxy herbicides (2,4-D and MCPA) has been studied through several bioassays using different testing times and biomass/substrate ratios. A fast biodegradability test using unacclimated activated sludge yielded no biodegradation of the herbicides in 24 h. The inherent biodegradability test gave degradation percentages of around 20–30 % for the nitrochlorinated herbicides and almost complete removal of the chlorophenoxy compounds. Long-term biodegradability assays were performed using sequencing batch reactor (SBR) and sequencing batch membrane bioreactor (SB-MBR). Fixed concentrations of each herbicide below the corresponding EC₅₀ value for activated sludge were used (30 mg L^?1 for diuron and atrazine and 50 mg L^?1 for 2,4-D and MCPA). No signs of herbicide degradation appeared before 35 days in the case of diuron and atrazine and 21 days for 2,4-D, whereas MCPA was partially degraded since the early stages. Around 25–36 % degradation of the nitrochlorinated herbicides and 53–77 % of the chlorophenoxy ones was achieved after 180 and 135 days, respectively, in SBR, whereas complete disappearance of 2,4-D was reached after 80 days in SB-MBR.     

A new bioseed for determination of wastewater biodegradability: analysis of the experimental procedure

A new bioassay proposed in the patent P201300029 was applied to a pre-treated wastewater containing a mixture of commercial pesticides to simulate a recalcitrant industrial wastewater in order to determine its biodegradability. The test uses a mixture of standardized inoculum of the lyophilized bacteria Pseudomonas putida with the proper proportion of salts and minerals. The results highlight that biodegradation efficiency can be calculated using a gross parameter (chemical oxygen demand (COD)) which facilitates the biodegradability determination for routine water biodegradability analysis. The same trend was observed throughout the assay with the dehydrated and fresh inoculums, and only a difference of 5 % in biodegradation efficiency (E _f) was observed. The obtained results showed that the P. putida biodegradability assay can be used as a commercial test with a lyophilized inoculum in order to monitor the ready biodegradability of an organic pollutant or a WWTP influent. Moreover, a combination of the BOD₅/COD ratio and the P. putida biodegradability test is an attractive alternative in order to evaluate the biodegradability enhancement in water pre-treated with advanced oxidation processes (AOPs).     

Steel slags in a landfill top cover – Experiences from a full-scale experiment

A full scale field study has been carried out in order to test and evaluate the use of slags from high-alloy steel production as the construction materials for a final cover of an old municipal landfill. Five test areas were built using different slag mixtures within the barrier layer (liner). The cover consisted of a foundation layer, a liner with a thickness of 0.7 m, a drainage layer of 0.3 m, a protection layer of 1.5 m and a vegetation layer of 0.25 m. The infiltration varied depending on the cover design used, mainly the liner recipe but also over time and was related to seasons and precipitation intensity. The test areas with liners composed of 50% electric arc furnace (EAF) slag and 50% cementitious ladle slag (LS) on a weight basis and with a proper consistence of the protection layer were found to meet the Swedish infiltration criteria of ?50 l (m² a)^?1 for final covers for landfills for non-hazardous waste: the cumulative infiltration rates to date were 44, 19 and 0.4 l (m² a)^?1 for A1, A4 and A5, respectively. Compared to the precipitation, the portion of leachate was always lower after the summer despite high precipitation from June to August. The main reason for this is evapotranspiration but also the fact that the time delay in the leachate formation following a precipitation event has a stronger effect during the shorter summer sampling periods than the long winter periods. Conventional techniques and equipment can be used but close cooperation between all involved partners is crucial in order to achieve the required performance of the cover. This includes planning, method and equipment testing and quality assurance.     

Growth Inhibition by Nitrocompounds of Selected Uric Acid-Utilizing Microorganisms Isolated from Poultry Manure

The overall objective of this study was to evaluate the potential ability of nitrocompounds to reduce ammonia volatilization by inhibiting uric acid–utilizing microorganisms. Experiment I was conducted to evaluate the effects of nitrocompounds on the growth of uric acid–utilizing microorganisms isolated from poultry manure during six-hour incubation. There were five treatments: (1) control, (2) 50 mM nitroethane, (3) 50 mM nitroethanol, (4) 50 mM nitropropanol, and (5) 50 mM nitropropionic acid. Optical density values of nitrocompounds were significantly lower than that of control at two, four, and six hours. Plate counts of uric acid–utilizing microorganisms after six-hour incubation exhibited that nitrocompounds greatly reduced the growth of these microorganisms except for the nitroethane (P < 0.05). The nitropropanol and nitropropionic acid treatments showed significantly higher inhibitory effects compared to the nitroethanol. Experiments II and III were conducted to evaluate inhibitory effects of nitrocompounds on growth of uric acid–utilizing microorganisms compared to non-nitrocompounds such as ethanol, propanol, and propionic acid. Experiments II and III consisted of seven treatments: (1) control, (2) nitroethanol, (3) nitropropanol, (4) nitropropionic acid, (5) ethanol, (6) propanol, and (7) propionic acid. The incubation times of Experiments II and III were 6 and 24 h, respectively. The nitrocompounds were significantly more successful in inhibiting growth of uric acid–utilizing microorganisms compared to those non-nitrocompounds. These results suggest that nitrocompounds exhibit potential to reduce ammonia volatilization in poultry manure by inhibiting growth of uric acid–utilizing microorganisms.     

A two-generational reproductive toxicity study of zinc in rats

A two-generation reproductive toxicity study of zinc chloride (ZnCl₂) was conducted in rats. F_o male and female rats were administered 0.00 (control), 7.50 (low), 15.00 (mid) and 30.00 (high) mg/kg/day of ZnCl₂. Selected F₁ male and female rats were exposed to the same doses received by their parents (F_o). Exposure of F₀ parental rats to ZnCl₂ showed significant reduction in fertility, viability (days 0 and 4), and the body weight of F₁ pups from the high-dose group but caused no effects on litter size, weaning index, and sex ratio. Similarly, the continued exposure of F₁ parental rats to ZnCl₂ also reduced fertility, liter size, viability (day 0), and the body weight of F₂ pups within the high-dose group but caused no effects on weaning index and sex ratio. Exposure of ZnCl₂ to F₀ and F₁ parental males resulted in a significant reduction in their body weights, and the F₀ and F₁ parental females did not show any significant difference in their body weights compared to their control groups. However, the postpartum dam weights of both F₀ and F₁ female rats were significantly reduced compared to their controls. Exposure of ZnCl₂ to F_o and F₁ generation parental rats did not produce any significant change of their clinical signs as well as their clinical pathology parameters, except the alkaline phosphotase (ALK) level, which showed an upward trend in both sexes of both generations. Exposure of ZnCl₂ to F₀ rats resulted in a reduction of brain, liver, kidney, spleen and seminal vesicles weights of males and in the spleen and uterus of females. Similarly, exposure of F₁ rats to ZnCl₂ also resulted in reduction of brain, liver, kidney, adrenal, spleen, prostate and seminal vesicles weights of males and in spleen and uterus of females. ZnCl₂ exposure resulted in grossly observed gastro-intestianla (GI) tract, lymphoreticular/hematopoietic, and reproductive tract lesions in parental rats in both generations. Reduced body fat was also recorded in F₁ parental rats.     

Treatment of wastewater from red and tropical fruit wine production by zeolite anaerobic fluidized bed reactor

A study of the anaerobic treatment of wastewaters derived from red (RWWW) and tropical fruit wine (TFWWW) production was carried out in four laboratory-scale fluidized bed reactors with natural zeolite as bacterial support. These reactors operated at mesophilic temperature (35°C). Reactors R1 and R2 contained Chilean natural zeolite, while reactors R3 and R4 used Cuban natural zeolite as microorganism support. In addition, reactors R1 and R3 processed RWWW, while reactors R2 and R4 used TFWWW as substrate. The biomass concentration attached to zeolites in the four reactors studied was found to be in the range of 44–46 g volatile solids (VS)/L after 90 days of operation time. Both types of zeolites can be used indistinctly in the fluidized bed reactors achieving more than 80%–86% chemical oxygen demand (COD) removals for organic loading rates (OLR) of up to at least 20 g COD/L d. pH values remained within the optimal range for anaerobic microorganisms for OLR values of up to 20 and 22 g COD/L d for RWWW and TFWWW, respectively. Toxicity and inhibition levels were observed at an OLR of 20 g COD/L d in reactors R1 and R3 while processing RWWW, whereas the aforementioned inhibitory phenomena were not observed at an OLR of 24 g COD/L d in R2 and R4, treating TFWWW as a consequence of the lower phenolic compound content present in this substrate. The volatile fatty acid (VFA) levels were always lower in reactors processing TFWWW (R2 and R4) and these values (< 400 mg/L, as acetic acid) were lower than the suggested limits for digester failure. The specific methanogenic activity (SMA) was twice as high in reactors R2 and R4 than in R1 and R3 after 120 days of operation when all reactors operated at an OLR of 20 g COD/L d.     

The effects of residual tetracycline on soil enzymatic activities and plant growth

A pot trial was carried out to investigate the adverse effects of tetracycline (TC) on soil microbial communities, microbial activities, and the growth of ryegrass (Lolium perenne L). The results showed that the presence of TC significantly disturbed the structure of microbial communities and inhibited soil microbial activities in terms of urease, acid phosphatase and dehydrogenase (p < 0.05). Plant biomass was adversely influenced by TC, especially the roots with a reduction of 40% when compared with the control. Furthermore, TC decreased the assimilation of phosphorus by the plant although the concentration of phosphorus was increased by 20% due to decreased plant biomass. TC seemed to increase the concentration of dissolved organic carbon (by 20%) in soil. The findings implied that the agricultural use of animal manure or fishpond sediment containing considerable amounts of antibiotics may give rise to ecological risks.     

Manure placement depth impacts on crop yields and N retained in soil

The objective of this study was to determine the impact of manure placement depth on crop yield and N retention in soil. Experimental treatments were deep manure injection (45 cm), shallow manure injection (15 cm), and conventional fertilizer-based management with at least three replications per site. Water infiltration, and changes in soil N and P amounts were measured for up to 30 months and crop yield monitored for three seasons following initial treatment. Deep and shallow manure injections differed in soil inorganic N distributions. For example, in the manure slot the spring following application, NO₃-N in the surface 60 cm was higher (p < .01) when injected 15 cm (21.4 μ g/g) into the soil than 45 cm (11.7 μ g/g), whereas NH₄-N had opposite results with shallow injection having less (p = 0.045) NH₄-N (102 μ g/g) than deep (133 μ g/g) injection. In the fall one year after the manure was applied, NO₃-N and NH₄-N were lower (p = 0.001) in the shallow injection than the deep injection. The net impact of manure placement on total N was that deep injection had 31, 59, and 44 more kg N ha^{? 1} than the shallow injection treatment 12, 18, and 30 months after application, respectively. Deep manure injection did not impact soybean (Glycine max L.) yield, however corn (Zea mays L.) yield increased if N was limiting. The higher corn yield in the deep injected treatment was attributed to increased N use efficiency. Higher inorganic N amounts in the deep injection treatment were attributed to reduced N losses through ammonia volatilization, leaching, or denitrification. Results suggest that deep manure placement in glacial till soil may be considered a technique to increase energy, N use efficiency, and maintain surface and ground water quality. However, this technique may not work in glacial outwash soils due to the inability to inject into a rocky subsurface.