Investigation of the inorganic and organic phosphorus forms in animal manure

The most viable way to beneficially use animal manure on most farms is land application. Over the past few decades, repeated manure application has shown adverse effects on environmental quality due to phosphorus (P) runoff with rainwater, leading to eutrophication of aquatic ecosystems. Improved understanding of manure P chemistry may reduce this risk. In this research, 42 manure samples from seven animal species (beef and dairy cattle, swine, chicken, turkey, dairy goat, horse, and sheep) were sequentially fractionated with water, NaHCO?, NaOH, and HCl. Inorganic (P(i)), organic (P(o)), enzymatic hydrolyzable (P(e); monoester-, DNA-, and phytate-like P), and nonhydrolyzable P were measured in each fraction. Total dry ash P (P(t)) was measured in all manures. Total fractionated P (P(ft)) and total P(i) (P(it)) showed a strong linear relationship with P(t). However, the ratios between P(ft)/P(t) and P(it)/P(t) varied from 59 to 117% and from 28 to 96%, respectively. Water and NaHCO? extracted most of the P(i) in manure from ruminant+horse, whereas in nonruminant species a large fraction of manure P was extracted in the HCl fraction. Manure P(e) summed over all fractions (P(et)) accounted for 41 to 69% of total P(0) and 4 to 29% of P(t). The hydrolyzable pool in the majority of the manures was dominated by phytate- and DNA-like P in water, monoester- and DNA-like P in NaHCO?, and monoester- and phytate-like P in NaOH and HCl fractions. In conclusion, if one assumes that the P(et) and P(it) from the fractionation can become bioavailable, then from 34 to 100% of P(t) in animal manure would be bioavailable. This suggests the need for frequent monitoring of manure P for better manure management practices.     

Isolation of mesotrione-degrading bacteria from aquatic environments in Brazil

Mesotrione is a benzoylcyclohexane-1,3-dione herbicide that inhibits 4-hydroxyphenyl pyruvate dioxygenase in target plants. Although it has been used since 2000, only a limited number of degrading microorganisms have been reported. Mesotrione-degrading bacteria were selected among strains isolated from Brazilian aquatic environments, located near corn fields treated with this herbicide. Pantoea ananatis was found to rapidly and completely degrade mesotrione. Mesotrione did not serve as a sole C, N, or S source for growth of P. ananatis, and mesotrione catabolism required glucose supplementation to minimal media. LC-MS/MS analyses indicated that mesotrione degradation produced intermediates other than 2-amino-4-methylsulfonyl benzoic acid or 4-methylsulfonyl-2-nitrobenzoic acid, two metabolites previously identified in a mesotrione-degrading Bacillus strain. Since P. ananatis rapidly degraded mesotrione, this strain might be useful for bioremediation purposes.     

Properties of alkali-activated systems with stone powder sludge

This article investigates the effects of stone powder sludge on the microstructure and strength development of alkali-activated fly ash and blast furnace slag mixes. Stone powder sludge produced from a crushed aggregate factory was used to replace fly ash and granulated blast furnace slag at replacement ratios of 0%, 10%, 20%, and 30% by mass. The unit weight and compressive strength of the samples were measured, and scanning electron microscopy/energy dispersive spectroscopy and X-ray diffraction (XRD) analyses were performed. The test results indicated that the compressive strength of alkali-activated blast furnace slag mixes using stone powder sludge was higher than that of the alkali-activated blast furnace slag control mix, but the compressive strength of alkali-activated fly ash mixes decreased with increasing replacement ratio of stone powder sludge. Microscopy results indicated that for alkaliactivated blast furnace slag samples, broken surfaces were more evident than for the alkali-activated fly ash samples. For all XRD diagrams, broad and diffuse peaks were observed around 2θ = 35° (d = 2.96–3.03 Å), implying amorphous or short-ordering structure phases.     

Ecotoxicity assessment of lipid regulators in water and biologically treated wastewater using three aquatic organisms

Background, aim, and scope  

The high consumption of blood lipid regulators is leading to frequent reports of the occurrence of fibrates in natural streams and wastewater effluents. This paper describes a study undertaken to evaluate the acute toxicity of bezafibrate, clofibric acid, gemfibrozil, and fenofibric acid, a metabolite of fenofibrate whose ecotoxicity has not been previously reported.     

PM2.5 and PM10: The influence of sugarcane burning on potential cancer risk

In Brazil, sugarcane fields are often burned to facilitate manual harvesting, and this burning causes environmental pollution from the large amounts of soot released into the atmosphere. This material contains numerous organic compounds such as PAHs. In this study, the concentrations of PAHs in two particulate-matter fractions (PM_2.5 and PM₁₀) in the city of Araraquara (SE Brazil, with around 200,000 inhabitants and surrounded by sugarcane plantations) were determined during the sugarcane harvest (HV) and non-harvest (NHV) seasons in 2008 and 2009. The sampling strategy included four campaigns, with 60 samples in the NHV season and 220 samples in the HV season. The PM_2.5 and PM₁₀ fractions were collected using a dichotomous sampler (10 L min^?1, 24 h) with Teflon? filters. The filter sets were extracted (ultrasonic bath with hexane/acetone (1:1 v/v)) and analyzed by HPLC/Fluorescence. The median concentration for total PAHs (PM_2.5 in 2009) was 0.99 ng m^?3 (NHV) and 3.3 ng m^?3 (HV). In the HV season, the total concentration of carcinogenic PAHs (benz(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene) was 5 times higher than in the NHV season. B(a)P median concentrations were 0.017 ng m^?3 and 0.12 ng m^?3 for the NHV and HV seasons, respectively. The potential cancer risk associated with exposure through inhalation of these compounds was estimated based on the benzo[a]pyrene toxic equivalence (BaP_eq), where the overall toxicity of a PAH mixture is defined by the concentration of each compound multiplied by its relative toxic equivalence factor (TEF). BaP_eq median (2008 and 2009 years) ranged between 0.65 and 1.0 ng m^?3 and 1.2–1.4 ng m^?3 for the NHV and HV seasons, respectively. Considering that the maximum permissible BaP_eq in ambient air is 1 ng m^?3, related to the increased carcinogenic risk, our data suggest that the level of human exposure to PAHs in cities surrounded by sugarcane crops where the burning process is used is cause for concern.     

Landfill mining from a deposit of the chlorine/organochlorine industry as source of dioxin contamination of animal feed and assessment of the responsible processes

In 1997, the Polychlorinated dibenzo-para-dioxin (PCDD)/Polychlorinated dibenzofuran (PCDF) concentrations in dairy products in Germany and other European countries increased. The PCDD/PCDF source was contaminated lime used in Brazilian citrus pulp pellets. The contaminated lime was mined from an industrial dump site. However, the detailed origin of the PCDD/PCDFs in the lime was not revealed. This paper investigates the contamination origin and describes the link between lime milk from the dumpsite of a chlorine/organochlorine industry and the contaminated lime. The contaminated lime stem from mining at the corporate landfill of Solvay Indupa in Sao Paulo. The landfill was used for 40 years for deposition of production residues and closed in 1996. The factory operated/operates at least two processes with potentially high PCDD/PCDFs releases namely the oxychlorination process for production of ethylene dichloride (EDC) and the chlor-alkali process. The main landfilled waste was lime milk (1.4 million tons) from the vinyl chloride monomer production (via the acetylene process) along with residues from other processes. The PCDD/PCDF fingerprint revealed that most samples from the chemical landfill showed an EDC PCDD/PCDF pattern with a characteristic octachlorodibenzofuran dominance. The PCDD/PCDF pattern of a Rio Grande sediment samples downstream the facility showed a chlor-alkali pattern with a minor impact of the EDC pattern. The case highlights that PCDD/PCDF- and persistent organic pollutants-contaminated sites need to be identified in a comprehensive manner as required by the Stockholm Convention (article 6) and controlled for their impact on the environment and human health. Landfill mining and reuse of materials from contaminated deposits should be prohibited.     

Determination of anti-anxiety and anti-epileptic drugs in hospital effluent and a preliminary risk assessment

In this study, an analytical methodology was developed for the determination of psycho-active drugs in the treated effluent of the University Hospital at the Federal University of Santa Maria, RS – Brazil. Samples were collected from point A (Emergency) and point B (General effluent). The adopted methodology included a pre-concentration procedure involving the use of solid phase extraction and determination by liquid chromatography coupled to mass spectrometry. The limit of detection for bromazepam and lorazepam was 4.9 ± 1.0 ng L⁻¹ and, for carbamazepine, clonazepam and diazepam was 6.1 ± 1.5 ng L⁻¹. The limit of quantification was 30.0 ± 1.1 ng L⁻¹, for bromazepam, clonazepam and lorazepam; for carbamazepine was 50.0 ± 1.8 ng L⁻¹ and was 40.0 ± 1.0 ng L⁻¹ for diazepam. The mean concentrations in the Emergency and General effluent treated currents were as follows: for bromazepam, 195 ± 6 ng L⁻¹ and 137 ± 7 ng L⁻¹; for carbamazepine, 590 ± 6 ng L⁻¹ and 461 ± 10 ng L⁻¹; for diazepam, 645 ± 1 ng L⁻¹ and 571 ± 10 ng L⁻¹; for lorazepam, 96 ± 7 ng L⁻¹ and 42 ± 4 ng L⁻¹; and for clonazepam, 134 ± 10 ng L⁻¹ and 57 ± 10 ng L⁻¹. A preliminary risk assessment was conducted: carbamazepine and diazepam require considerable attention owing to their environmental toxicity. The occurrence of these psychoactive-drugs and the environmental risks that they pose demonstrated the need for a more efficient treatment system. As far we are aware, there have been no comparable studies to this on the hazards of hospital effluents in Brazil, and very few that have carried out a risk assessment of psycho-active drugs in hospital effluent in general.     

Earthworm ecotoxicological assessments of pesticides used to treat seeds under tropical conditions

Ecotoxicological laboratory tests (lower-tier tests) are fundamental tools for assessing the toxicity of pesticides to soil organisms. In this study, using these tests under tropical conditions, we quantified the impact of the insecticides imidacloprid, fipronil, and thiametoxam, and the fungicides captan and carboxin + thiram, all of which are used in the chemical treatment of crop seeds, on the survival, reproduction, and behavior of Eisenia andrei (Oligochaeta). With the exception of imidacloprid, none of the pesticides tested caused mortality in E. andrei in artificial soils. The LC₅₀ of imidacloprid was estimated as 25.53 mg active ingredient kg^?1 of dry soil. Earthworm reproduction rates were reduced by imidacloprid (EC₅₀ = 4.07 mg kg^?1), fipronil (EC₂₀ = 23.16 mg kg^?1), carboxin + thiram (EC₅₀ = 56.38 mg kg^?1), captan (EC₅₀ = 334.84 mg kg^?1), and thiametoxam (EC₅₀ = 791.99 mg kg^?1). Avoidance behavior was observed in the presence of imidacloprid (AC₅₀ = 0.11 mg kg^?1), captan (AC₅₀ = 33.54 mg kg^?1), carboxin + thiram (AC₅₀ = 60.32 mg kg^?1), and thiametoxam (AC₅₀ = >20 mg kg^?1). Earthworms showed a preference for soils with the insecticide fipronil. Imidacloprid was the most toxic of the substances tested for E. andrei. The avoidance test was the most sensitive test for most pesticides studied, but results varied between pesticides. These results offer new insights on the toxicity of pesticides used to treat seeds in tropical regions. However, they should be complemented with higher-tier tests in order to reduce the uncertainties in risk assessment.     

Comparing the sensitivity of soil invertebrates to pesticides with that of Eisenia fetida

The sole routine testing of the standard earthworm Eisenia fetida for the terrestrial risk assessment of pesticides has been under much debate since other soil invertebrates may be more sensitive than this standard test species. However, the very low availability of laboratory toxicity data for taxa other than E. fetida has greatly hampered sensitivity comparisons. In the present study, the relative tolerance (T_rel) approach was used to enable comparing toxicity thresholds obtained from the US-EPA ECOTOX database, for main terrestrial taxonomic groups and pesticidal types of action (insecticides, fungicides, herbicides, and other) separately. Analyses confirmed previously reported lower and higher sensitivity of collembolans to fungicides and insecticides, respectively. However, various other discrepancies in susceptibility relative to E. fetida were encountered as indicated by species sensitivity distributions and/or calculated 95% confidence intervals of T_rel values. Arachnids and isopods were found to be more sensitive to insecticides, and nematodes to fungicides, as compared to E. fetida. Implications of study findings for the terrestrial risk assessment of pesticides are discussed.     

Concentrations of PCDD/PCDF in soil close to a secondary aluminum smelter

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) were analyzed in samples of the emissions from a secondary aluminum smelter (ALS) and soil samples around the plant. The purpose was to estimate the impact of the emissions on the surrounding environment.PCDD/F soil concentrations were higher in the proximity of the plant, exceeding the limit adopted in Italy in soils for green areas and residential uses and the upper limit of several reference concentrations. The most contaminated sites were less than 500 m from the plant and the dioxin concentration with the distance from the ALS.Principal component analysis (PCA) showed that emissions from the ALS were the source of PCDD/F contamination in the soils closest to the plant. Multivariate data analyses such as PCA are therefore useful to identify sources of emission causing contamination.