Investigation of organic xenobiotic transfers,partitioning and processing in air-soil-plant systems using a microcosm apparatus. Part II: comparing the fate of chlorobenzenes in grass planted soil

A microcosm system was used to investigate and compare transfers of 14C labeled-1,2-dichlorobenzene (DCB), 1,2,4-trichlorobenzene (TCB) and hexachlorobenzene (HCB) in an air-soil-plant system using single grass tillers planted into spiked soil. This study was the second phase of a development investigation for eventual study of a range of xenobiotic pollutants. Recoveries from the system were excellent at >90%. The predominant loss pathway for 14C labeled-1,2-DCB and 1,2,4-TCB was volatilisation with 85% and 76% volatilisation of parent compound and volatile metabolites over 5 weeks respectively. Most of the added label in the hexachlorobenzene spiked system remained in soil. Mineralisation was <1% for all compounds. 14C plant burdens expressed as microg parent compound/g plant fresh weight were significant and suggest that plant uptake of chlorobenzenes from soil may be an important exposure pathway for grazing herbivores. Both shoot and root uptake of 14C was detected, with foliar uptake of volatilised compounds dominating shoot uptake, and being greatest in TCB spiked systems. The microcosm is shown as potentially an ideal system with which to investigate organic xenobiotic partitioning in air-soil-plant systems to improve understanding of the equilibria and kinetics of exchanges. However, limitations imposed by the lab based conditions must be recognized and data should be compared with field based data sets as a consequence.     

The role of humic substances in chromium sorption onto natural organic matter (peat)

To elucidate mechanisms of Cr³⁺ sorption onto the unaltered solid natural organic matter, the comparative studies of this ion binding from a solution at pH 4.0 onto three selected particle size fractions: 2000–1000 μm, 630–200 μm and 63–20 μm of markedly different HS content and structure, separated by a wet sieving from an overall sample of peat (Brushwood Peat Humus) were carried out. Comparable patterns of COOH groups and CEC_t confirmed that for cation exchange capacity were responsible mainly cations connected with COO⁻ functional groups. It was though found that aliphatic acids in the solid state did not take part in Cr³⁺ binding, thus the finest studied fraction 63–20 μm of the highest contents of functional groups showed the lowest sorption capacity for Cr³⁺, while similar patterns of sorbed Cr³⁺, soluble HS content and base CEC₀ indicated that these parameters were directly interrelated. The base ion exchange processes determined by CEC₀ (with Ca²⁺ as a predominant exchangeable cation) appeared to be not the major mechanisms responsible for Cr³⁺ sorption. For this metal, strong binding to insoluble large molecular weight organic pool two- to threefold prevailed over the ion exchange processes. Very low acid desorption indicated generally low mobility of Cr³⁺-organic compounds.     

Can aquatic distribution of human pharmaceuticals be related to pharmacological data?

The recognition of pharmaceuticals as significant environmental contaminants has only been a recent phenomenon. Therefore there is a paucity of data relating to the fate and effects of pharmaceuticals once they enter an aquatic receiving system. The amount of work that needs to be done in terms of risk assessment for pharmaceuticals required by regulatory agencies is substantial. This paper has determined the environmental partitioning coefficient (K_d) of 13 diverse human pharmaceuticals in three model systems of differing combinations of solid phases and solutions. The K_d values were then compared with distribution values of the pharmaceuticals in the human body determined from pharmacological studies. This was done to assess the functional relationship between K_d and distribution values in the human body (V_D). K_d values ranged from 3 to 2450 L kg⁻¹. Regression coefficients ranged from r² = 0.62–0.72, indicating that V_D values are a useful indicator for the K_d values of the tested pharmaceuticals within the batch sorption systems. The relationship between K_d and V_D should therefore be further explored to determine whether this relationship can be applied to a broader range of pharmaceuticals in more diverse environmental systems. Exploiting available human pharmacological data in such a way would be of great benefit in prioritising human pharmaceuticals as environmental contaminants in the risk assessment process.     

Copper complexation by tannic acid in aqueous solution

The speciation of titrated copper in a dissolved tannic acid (TA) solution with an initial concentration of 4 mmol organic carbon (OC)/l was investigated in a nine-step titration experiment (Cu/OC molar ratio = 0.0030–0.0567). We differentiated between soluble and insoluble Cu species by 0.45 μm filtration. Measurements with a copper ion selective electrode (ISE) and diffusive gradients in thin films (DGT) were conducted to quantify unbound Cu(II) cations (‘free’ Cu) and labile soluble Cu complexes. For the DGT measurements, we used an APA hydrogel and a Chelex 100 chelating resin (Na form). Insoluble organic Cu complexes (>0.45 μm) was the dominant Cu species for Cu/OC = 0.0030–0.0567 with a maximum fraction of 0.96 of total Cu. At Cu/OC > 0.0100, Cu-catalysed degradation of aggregate structures resulted in a strong increase of free Cu and (labile) soluble Cu complexes with a maximum fraction of 0.28 and 0.32 of total Cu, respectively. Labile (i.e. DGT-detectable) soluble Cu complexes had a relatively high averaged diffusion coefficient (D) in the APA hydrogel (3.50 × 10⁻⁶– 5.58 × 10⁻⁶ cm² s⁻¹).     

Broad range analysis of endocrine disruptors and pharmaceuticals using gas chromatography and liquid chromatography tandem mass spectrometry

Endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) have been globally detected in impacted natural waters. The detection of trace quantities of EDCs and PPCPs in the environment is of great concern since some of these compounds have known physiological responses at low concentrations. EDCs can have a wide range of polarities, acidic and basic moieties, and exist in trace quantities, which often requires numerous complex extractions, large sample collection volumes, and multiple instrumental analyses. A comprehensive method has been developed allowing for the analysis of 58 potential EDCs in various water matrices using a single solid-phase extraction (SPE) of a 1 L sample with subsequent analyses using both gas chromatography and liquid chromatography, each coupled with tandem mass spectrometry (GC–MS/MS and LC–MS/MS). Instrument detection limits ranged between 0.12–7.5 pg with corresponding method reporting limits of 1–10 ng l⁻¹ in water. Recoveries for most compounds were between 50% and 112% with good reproducibility (RSD 6–22%).     

The influence of untreated wastewater to aquatic communities in the Balatuin River,The Philippines

A risk assessment of chemical constituents in rivers that receive untreated wastewater should take into account the adverse effects of increased biological oxygen demand (BOD), ammonia and reduced dissolved oxygen (DO). This concept was tested via a field study in the Balatuin River, The Philippines, where the influence of physical and chemical factors, including the consumer product chemical linear alkylbenezene sulfonate (LAS), to aquatic communities (algae, invertebrates, fish) was determined. Periphytic algae were found to be insensitive to high BOD (>10 mg/l) and ammonia (>0.01 mg unionized NH(3)/l), concentrations from organically enriched untreated wastewater discharges. However, taxa richness and abundance of macroinvertebrates were influenced greatly by the discharges. Where BOD and ammonia concentrations were elevated, the dominant taxa were oligochaete worms and chironominds. Fish and crustaceans (freshwater crabs and prawns) were found only in sites with the least BOD concentrations (furthest upstream and downstream). The maximum concentration of LAS (0.122 mg/l) was less than that expected to affect 5% of taxa (0.245 mg/l), whereas exceedences of DO and ammonia criteria were observed in several sites. The lack of recovery observed was attributed to influences of low DO, high ammonia and poor colonization from upstream and downstream reaches due to organically-enriched discharges     

Pressurized liquid extraction of six tetracyclines from agricultural soils

Veterinary antibiotics used in agriculture can be introduced into the environment through land application of animal manure, accumulating in soils and groundwaters and posing a significant risk to human health and animal well-being. As the analysis of tetracyclines in soil is challenging due to their strong interaction with soil minerals and organic carbon, the objective of this study was to develop a reliable and reproducible method for quantitative analysis of chlortetracycline and oxytetracycline, and their respective metabolites in soils. A method based on pressurized liquid extraction (PLE) with in-cell clean-up was developed for the extraction of chlortetracycline and oxytetracycline and four likely metabolites from a set of four soils. Optimized conditions included a cell size of 22?mL, soil loading of 5?g, pH of 8.0, methanol:water ratio of 3:1, 50?°C, and two cycles. Soil extracts were analysed by high-performance liquid chromatography (HPLC) coupled with ion trap mass spectrometry (MS). Recoveries of seven tetracyclines from soil ranged from 41% to 110%. The limits of detection for tetracyclines were 0.08–0.3 µg g^?1 soil, and intra- and inter-day variation ranged from 0.12–0.34%. The proposed PLE method is suitable for quantification of tetracyclines in agricultural soils at typical concentrations expected in contaminated environments.     

Trace elements and microbiological parameters in farmed Nile tilapia with emphasis on muscle,water, sediment and feed

Fish may bioaccumulate contaminants from the aquatic environment and extend them to the food chain provoking risks to human health. This study evaluated the microbiological parameters of the pond´s water and trace elements concentrations in samples of water, sediment, feed and muscle of farmed Nile tilapia used for human consumption in southern Brazil. A total of 240 fish were collected from 12 tilapia farms. Sediment, tank water and dry ration used in the animals' diet were collected for analysis. Analysis were performed by Energy Dispersion X-ray Fluorescence (EDXRF), Inductively Coupled Plasma Mass Spectrometer (ICP-MS), Induced Coupled Plasma Optical Emission Spectrometer (ICP-OES), and Atomic Absorption Spectrometer (AAS-VGA). In addition, the microbiological analysis of the water was carried out. The concentrations of Se, I, Fe, Cu and Zn in fish muscle were higher than the recommended by the Brazilian legislation, considering the advised daily intake for adults. The arsenic element had concentrations above the limit stipulated by the present Brazilian legislation, observed in all samples of muscle, sediment and tank water highlighting a possible environmental and fish contamination by the toxic element. Moreover, the arsenic concentration in the water presented a positive correlation (ρ?=?0.33) with arsenic in the muscle, suggesting that tilapia is a good environmental bioindicator, once they properly reflect the levels of arsenic in the water. It is suggested to perform an arsenic speciation for quantification of the inorganic form and accurate assessment of the degree of toxicity in the muscle samples and risks it can bring to human health. Regarding the other potentially toxic elements (Hg, Pb and Cd), and microbiological analysis of water it was verified that the consumption of the fish in question does not raise risks, since the values are within a quality benchmark established by law. The concentration of total and fecal coliforms in pond´s water in the facilities was in agreement with the microbiological indexes required by the legislation of CONAMA class II. Western region presented the lowest concentrations of fecal coliforms when compared to the other regions. There was no significant difference in the microbiological counts of total heterotrophic bacteria, Vibrio spp. and Pseudomonas spp. among the regions.     

Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

Determination of the residue dynamics and dietary risk of thiamethoxam and its metabolite clothianidin in citrus and soil by LC-MS/MS

A modified quick, easy, cheap, effective, rugged and safe (QuEChERS) method was developed for the determination of thiamethoxam and its metabolite clothianidin in citrus (including the whole citrus, peel and pulp) and soil samples by liquid chromatography-tandem mass spectrometry. The sample was extracted with acetonitrile and purified with octadecylsilane. The detection limits of both compounds were 0.0001–0.0002?mg kg^–1, while the limit of quantification of thiamethoxam was 0.002?mg kg^–1 and the limit of quantitation of metabolites was 0.001?mg kg^–1. The recovery was 70.37%–109.76%, with inter-day relative standard deviations (RSD) (n?=?15) values ≤9.46% for the two compounds in the four matrices. The degradation curve of thiamethoxam in whole citrus and soil was plotted using the first-order kinetic model. The half-life of the whole citrus was 1.9–6.2?days, and the half-life of the soil was 3.9–4.2?days. The terminal residue of thiamethoxam (the sum of thiamethoxam and clothianidin, expressed as thiamethoxam) was found to be concentrated on the peel. The final residual amount of thiamethoxam in the edible portion (pulp) was less than 0.061?mg kg^–1. The risk quotient values were all below 1, indicating that thiamethoxam as a citrus insecticide does not pose a health risk to humans at the recommended dosage.