Toxicity of abamectin and doramectin to soil invertebrates

This study aimed at determining the toxicity of avermectins to soil invertebrates in soil and in faeces from recently treated sheep. Abamectin was more toxic than doramectin. In soil, earthworms (Eisenia andrei) were most affected with LC50s of 18 and 228 mg/kg dry soil, respectively, while LC50s were 67-111 and >300 mg/kg for springtails (Folsomia candida), isopods (Porcellio scaber) and enchytraeids (Enchytraeus crypticus). EC50s for the effect on reproduction of springtails and enchytraeids were 13 and 38 mg/kg, respectively for abamectin, and 42 and 170 mg/kg for doramectin. For earthworms, NOEC was 10 and 8.4 mg/kg for abamectin and doramectin effects on body weight. When exposed in faeces, springtails and enchytraeids gave LC50s and EC50s of 1.0-1.4 and 0.94-1.1 mg/kg dry faeces for abamectin and 2.2->2.4 mg/kg for doramectin. Earthworm reproduction was not affected. This study indicates a potential risk of avermectins for soil invertebrates colonizing faeces from recently treated sheep.     

Platinum and Palladium transfer to milk, organs and tissues after a single oral administration to lactating goats

Platinum (Pt) and Palladium (Pd) are massively used in catalytic converters, emitted with exhaust fumes and deposited on roadsides in particle sizes. If they are ingested by ruminants grazing in agricultural fields located along roads they may enter the food chain. The objective of this study is to assess the potential transfer of Pt (PtCl(2)) and Pd (PdCl(2)) towards milk, tissues (muscle) and organs (kidney, liver and mammary gland). Three lactating goats received orally a single dose of 200mg of Pd and 200mg of Pt at the beginning of the experiment. The milk was collected each day during eight days. On the eighth day, organs and tissues were sampled to analyse the metal concentrations by ICP-MS (quantification limit of 0.25ng/g for Pd and Pt, detection limit of 0.08ng/g). The experiment demonstrated a significant transfer of Pd and Pt to kidney. The detected concentration was, respectively, of 73.9ng/g DW and 268.5n/g DW (factor 22 and factor 73 compared to the control kidney). The amounts of metals were : in the liver,18.1ng/g DW for the Pd and 8.1ng/g DW for the Pt, in the mammary gland, 14.9ng/g DW fort the Pd and 2.5ng/g DW for the Pt and in the muscle, 4.9ng/g DW for the Pd and 0.6ng/g DW for the Pt. The Pd concentration detected in milk was higher (from 5ng/g DW to 9ng/g DW) than in control milk but the transfer factor remained very low (0.02%). The Pt in milk could not be detected because it was below the quantification limit (<0.25ng/g DW).     

A non-absorbable dietary fat substitute enhances elimination of persistent lipophilic contaminants in humans.

For individuals contaminated with persistent lipophilic pollutants, there is an urgent need for a therapy to enhance contaminant elimination from the body and hence reduce long term exposure. This study investigated the possibility of enhancing the excretion of native chemical via the faeces by augmenting the lipophilic properties of the faeces with the non-absorbable lipid substitute olestra. The faecal excretion of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and hexachlorobenzene (HCB) was measured in 3 volunteers. The excretion while eating an olestra-free diet was compared with the excretion while eating a diet supplemented wit 25 g/d of olestra. The excretion while on the olestra diet was higher by a factor of 1.5-11, depending on the compound. This resulted from higher concentrations of the contaminants in the faeces and higher excretion of faeces dry mass due to the food additive. Using 2,3,7,8-Cl4DD as an example, it was estimated that ingestion of 25 g/d of olestra would more than double the overall rate of elimination of this compound from the body. It is concluded that regular consumption of olestra may provide a therapeutic approach for reducing the body burden of persistent lipophilic contaminants.     

Uptake and enantioselective elimination of chlordane compounds by common carp (Cyprinus carpio, L.)

An analytical method involving supercritical fluid extraction (SFE) followed by a two-dimensional gas chromatography (2D-GC) analysis was developed to determine the concentration (first GC) and enantiomeric ratio (second GC) of cis- and trans-chlordanes at the ppb (ng/g) level in fish tissue. The SFE method allowed concentration of the compounds of interest, and reduced the number of extraction and sample clean-up manipulations as compared to classical solvent extraction techniques. Four hundred common carp fingerling (Cyprinus carpio, L.) were exposed for three days to water containing 5 ppb (5 ng/g) technical grade chlordane containing about 1 ppb of chlordane isomers. The fish concentrated the pesticides more than 200 times (162 and 312 ng/g of cis- and trans-chlordane, respectively). However, the uptake is not enantioselective. The concentration of the principle constituents and their enantiomeric ratio was followed during a fifty days growth period in chlordane free water. The first order decay of concentration was observed with a half time of about 18 days for both the cis- and trans-chlordane isomers. However it was found that the enantiomeric ratio of the trans-chlordane was significantly altered during this short period of time, decreasing from ER=1 to ER=0.7, while no enantiomeric changes were observed for the cis-chlordane. It seems that the (-)-trans-chlordane is metabolized significantly faster (t(1/2-)=15 days) in the river carp fish than the (+)-trans-enantiomer (t(1/2+)=20 days).     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

Leaching of trifluralin,metolachlor, and metribuzin in a clay loam soil of Louisiana

Trifluralin[2,6-dinitro-N,N-dipropyl-4-(trifluormethyl)benzenamine], metolachlor[2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide], and metribuzin[4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)one] were applied in field plots located on a Commerce clay loam soil near Baton Rouge, Louisiana at the rate of 1683 g/ha, 2759 g/ha and 609 g/ha, respectively. The half-lives of trifluralin, metolachlor, and metribuzin in the top 0-15 cm soil depth were found to be 54.7 days, 35.8 days and 29.8 days, respectively. The proportion of trifluralin, metolachlor, and metribuzin in the top 0-15 cm soil depth was 94.7%, 86.6%, and 75.4%, respectively of that found in the top 0-60 cm soil depth 30 days after application. Trifluralin concentrations were within a range of 0.026 ng/mL to 0.058 ng/mL in 1 m deep well water, and between 0.007 ng/mL and 0.039 ng/mL in 2 m deep well water over a 62 day period after application. Metolachlor concentrations in the 1 m and 2 m wells ranged from 3.62 ng/mL to 82.32 ng/mL and 8.44 ng/mL to 15.53 ng/mL, respectively. Whereas metribuzin concentrations in the 1 m and 2 m wells ranged from 0.70 ng/mL to 27.75 ng/mL and 1.71 ng/mL to 3.83 ng/mL, respectively. Accordingly, trifluralin was found to be strongly adsorbed on the soil and showed negligible leaching. Although metolachlor and metribuzin were also both readily adsorbed on the soil, their leaching potential was high. As a result, in the clay loam soil studied, metribuzin concentration in groundwater with shallow aquifers is likely to exceed the 10 mg/L US Environmental Protection Agency (EPA) advisory level for drinking water early in the application season, whereas trifluralin and metolachlor concentrations are expected to remain substantially lower than their respective 2 ng/mL and 175 ng/mL EPA advisory levels.     

Residues and dissipation kinetic of abamectin,chlorfenapyr and pyridaben acaricides in green beans (Phaseolus vulgaris L.) under field conditions using QuEChERS method and HPLC

Abstract

The current study estimated the dissipation rates of abamectin, chlorfenapyr and pyridaben acaricides in pods of green beans (Phaseolus vulgaris L.) under field conditions in Egypt. Pesticides were extracted and cleaned-up by QuEChERS method and were analyzed by HPLC. The dissipation of these acaricides followed the first order kinetics model with half-life (t_1/2) values 1.00, 3.50 and 1.50?days for abamectin, chlorfenapyr and pyridaben, respectively. The lowest residues, at different time intervals of field application rate of each pesticide, were observed with abamectin followed by pyridaben and then chlorfenapyr. Pre-harvest intervals (PHIs) were 10.00, 13.50 and 6.00?days for abamectin, chlorfenapyr and pyridaben, respectively and were below the established European maximum residue limits (EU MRLs) 10–14, 14–21 and 7–10?days after application, respectively. If the fresh pods will be consumed after harvest, it is expected that the presence of these pesticides in the food will have a negative impact on human health. Therefore, the elimination of the residues of these harmful pesticides must be carried out.     

Minimal transmission of zearalenone to milk of dairy cows

Milk and plasma levels of zearalenone (ZEN), alpha-zearalenol (alpha-ZEL), beta-zearalenol (beta-ZEL) and conjugated metabolites were determined after feeding lactating cows with ZEN. In those instances where ZEN and alpha- and beta-ZEL were detected in milk or plasma, they occurred only as conjugates hydrolysable by treatment with a mixture of beta-glucuronidase and aryl sulfatase. With studies where 50 or 165 mg was fed daily to three cows for 21 day periods, neither dosage showed the presence of ZEN or metabolites in either milk or plasma (detection limits: milk, 0.5 ng/ml, ZEN, alpha-ZEL; 1.5 ng/ml, beta-ZEL; plasma, 2-3 times higher). A dose of 544.5 mg zearalenone per day given to a single cow for 21 days yielded maximum concentrations of only 2.5 ng ZEN/ml and 3.0 ng alpha-ZEL/ml in the milk. In plasma, up to 3 ng ZEN/ml could be detected during the initial 4 days of treatment. At a dose of 1.8 g of zearalenone given over a one day feeding period, maximum milk levels of 4.0 ng ZEN/ml, 1.5 ng alpha-ZEL/ml, and 4.1 ng beta-ZEL/ml were observed during the initial 2 days; corresponding maximum levels after a one day dose of 6.0 g zearalenone were 6.1, 4.0 and 6.6 ng/ml milk on days 2-3. In plasma, peak ZEN concentrations (9 and 13 ng/ml at the lower and higher one-day doses, respectively) occurred 12 hr after initial dosing, and declined to negligible levels by days 5-7. Neither alpha- nor beta-ZEL were detected in plasma. Since measurable levels required very high oral doses of ZEN, milk would not normally pose a human health hazard as a result of feeding rations containing ZEN to lactating dairy cows.     

Butyltins in water, biofilm, animals and sediments of the west coast of India

Biofilm, fish, oyster, mussel, clam, surface seawater, suspended particulate matter (SPM), and sediment samples were collected from marine and/or estuarine waters of the west coast of India. These samples were analysed for butyltin derivatives such as dibutyltin (DBT) and tributyltin (TBT). The concentrations DBT plus TBT varied between 2.4 and 8.3, 163 and 363 ng/l, 5 and 2853 ng/g dry wt in the SPM, seawater and sediment samples, respectively, of the Marmugao harbour. The values of DBT plus TBT ranged between 0.60 and 29, 123 and 242 ng/l and 1.4 and 65 ng/g dry wt in SPM, water and sediment samples, respectively, collected from the Mandovi estuary. In the Dona Paula Bay the DBT plus TBT varied from 10 to 89 ng/l in surface seawater, and TBT from 10 to 513 ng/g in biofilm samples. For the coastal sediment samples the concentration of DBT plus TBT ranged between 36 and 133 ng/g dry wt of sediment. For the animal samples the DBT plus TBT ranged between 58 and 825 ng/g dry wt of the tissue. Mussel tissues contained the highest amount of DBT plus TBT (825 ng/g dry wt tissue), whereas highest TBT concentration was recorded in the oyster (732 ng/g dry wt). TBT was generally the most abundant butyltin compound in most of the samples suggesting fresh inputs and/or less degradation of TBT. A wide range of the observed butyltin concentrations suggests the presence of localized areas of contamination. Leaching of tributyltin-containing antifouling paints from the ocean going ships, fishing and recreational boats, barges, and the inputs of TBT from the Goa shipyard and dry dock facility situated in the harbour are the probable sources of the DBT and TBT in the samples of the west coast of India. Higher levels of TBT were observed in biofilm relative to that in the surrounding seawater. When fed on TBT contaminated biofilm of the diatom Navicula subinflata, butyltin concentrations in the clam Paphia malabarica increased over the period of feeding suggesting the importance of biofilm in the transfer of butyltins to higher group of organisms.     

Occurrence of tributyltin (TBT)-resistant bacteria is not related to TBT pollution in Mekong River and coastal sediment: with a hypothesis of selective pressure from suspended solid

Tributyltin (TBT) is organotin compound that is toxic to aquatic life ranging from bacteria to mammals. This study examined the concentration of TBT in sediment from and near the Mekong River and the distribution of TBT-resistant bacteria. TBT concentrations ranged from <2.4 to 2.4 ng/g (dry wt) in river sediment and <2.4-15 ng g(-1) (dry wt) in harbor sediment. Viable count of total bacteria ranged from 2.0 x 10(4) to 1.4 x 10(7)cfu/g, and counts of TBT-resistant bacteria ranged <1.0 x 10(2) to 2.5 x 10(4)cfu/g. The estimated occurrence rate of TBT-resistant bacteria ranged from <0.01 to 34% and was highest in upstream sites in Cambodia. The occurrences of TBT in the sediment and of TBT-resistant bacteria were unrelated, and chemicals other than TBT might induce TBT resistance. TBT-resistant bacteria were more abundant in the dry season than in the rainy season. Differences in the selection process of TBT-resistant bacteria between dry and rainy seasons were examined using an advection-diffusion model of a suspended solid (SS) that conveys chemicals. The estimated dilution-diffusion time over a distance of 120 km downstream from a release site was 20 days during dry season and 5 days during rainy season, suggesting that bacteria at the sediment surface could be exposed to SS for longer periods during dry season.     

Congener distribution of polybrominated diphenyl ethers in feral carp (Cyprinus carpio) from the Llobregat River, Spain

Feral carp were collected at two Spanish rivers, Anoia and Cardener, showing PBDE levels from 29 to 638 ng/g lipid weight (lw) and from 54 to 744 ng/g lw, respectively. Sediments were also collected, showing PBDE contamination between 2 and 10 ng/g dry weight (dw). Differences in PBDE profiles between sediments and fish were noticed. Contribution of BDE-47 in sediment was up to 11%, whereas it contributed 37-90% of PBDEs in fish. Similar results were observed for BDE-154, which was only detected in one sediment sample, but presented high contribution in carp. In contrast, BDE-99 contributed up to 32% in sediments, but it was not detected in fish. Similar results were observed for BDE-153, BDE-183 and BDE-209. The main reason for their concentration decrease or absence in biota may be due to low bioavailability potential or due to biotransformation processes.     

Depuration of copper and zinc by green oysters and blue mussels of Taiwan

This paper describes depuration processes of copper and zinc in green oysters (Crassostrea gigas) and in blue mussels (Mytilus smarangdium) collected from an environment with heavy copper contamination, and then transferred to natural clean seawater. Results show that the total loss of copper content per oyster is an exponential function of exposure time for the first 6 days with a depuration rate of 351 microg g(-1) day(-1) and then levels off. During this exponential decrease period approximately 67% of the copper accumulated in green oysters was depurated. However, when the copper contents in the oysters decreased from 2225 +/- 111 microg g(-1) to 344 +/- 18.7 microg g(-1) the depuration rates decreased from 245 microg g(-1) day(-1) to 0.08 microg g(-1) day(-1). This means that green oysters had a 16-fold higher copper depuration rate (351 microg g(-1) day(-1)) than normal oysters (21.5 microg g(-1) day(-1)) for the first 6 days. However, the depuration of accumulated copper and zinc by the mussels was a fast process in natural clean seawater. About 91% of the accumulated copper was lost during the first 6-day period; copper contents declined from 20.2 +/- 3.41 microg g(-1) to 1.80 +/- 0.21 microg g(-1). Only 36% of the accumulated zinc was lost during a depuration period of 6 days. Calculations show that the biological half-lives of copper in green and normal oysters were 11.6 and 25.1 days, respectively. The biological half-lives of zinc in green and normal oysters were 16.7 and 30.1 days, respectively. In spite of the relatively low initial copper content in blue mussels being 20.2 +/- 3.41 microg g(-1), the biological half-life is only 6.40 days. From these results it is important to emphasise that the fastest turnover rate is for copper in blue mussels. However, zinc is more retentive in blue mussels than copper.     

Persistence and Changes in Bioavailability of Dieldrin, DDE, and Heptachlor Epoxide in Earthworms Over 45 Years

The finding of dieldrin (88 ng/g), DDE (52 ng/g), and heptachlor epoxide (19 ng/g) in earthworms from experimental plots after a single moderate application (9 kg/ha) 45 years earlier attests to the remarkable persistence of these compounds in soil and their continued uptake by soil organisms. Half-lives (with 95 % confidence intervals) in earthworms, estimated from exponential decay equations, were as follows: dieldrin 4.9 (4.3–5.7) years, DDE 5.3 (4.7–6.1) years, and heptachlor epoxide 4.3 (3.8–4.9) years. These half-lives were not significantly different from those estimated after 20 years. Concentration factors (dry weight earthworm tissue/dry weight soil) were initially high and decreased mainly during the first 11 years after application. By the end of the study, average concentration factors were 1.5 (dieldrin), 4.0 (DDE), and 1.8 (heptachlor epoxide), respectively.     

Fate and availability of glyphosate and AMPA in agricultural soil

The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT₅₀ values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, ¹⁴C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 ± 0.002% and 0.005 ± 0.001% of the applied radioactivity was measured in rape and barley, respectively.     

Accumulation, tissue-specific distribution and debromination of decabromodiphenyl ether (BDE 209) in European starlings (Sturnus vulgaris)

In this study we investigated the accumulation, tissue-specific distribution and possible debromination of BDE 209 in a terrestrial songbird species, the European starling, using silastic implants as a method of exposure. BDE 209 accumulated in the blood of the exposed starlings to a mean peak concentration of 16+/-4.1 ng/ml on day 10. After this peak, there was a decline to 3.3+/-0.4 ng/ml blood at the end of the exposure period of 76 days, which suggests elimination of BDE 209. In the exposed group, the muscle concentrations (461 ng/g lipid weight [lw], 430 ng/g lw) were about twofold those in liver (269 ng/g lw, 237 ng/g lw). In addition to BDE 209, other PBDE congeners, particularly octa- and nonaBDEs, were also present in the muscle and liver, suggesting bioformation from BDE 209. To our knowledge, these results are the first indications for the debromination of BDE 209 in birds.     

Excretion stereoselectivity of triticonazole in rat urine and faeces

Abstract

The purpose of this study was to study the excretion stereoselectivity of triticonazole enantiomers in rat urine and faeces. Six male Sprague-Dawley (SD) rats were administrated 50?mg/kg rac-triticonazole. Rats urine and faeces were separately and quantitatively collected at the following intervals: 0–3, 3–6, 6–9, 9–12, 12–24, 24–36 and 36–48?h. The faeces samples were homogenized in an aqueous solution containing 0.2% DMSO at the ratio of 1?g: 40?mL. An aliquot of 100?μL rats urine or faeces homogenate was spiked and mixed with 6.0?μL of 1.00?μg/mL flusilazole as an internal standard. The triticonazole enantiomers in urine and faeces were determined by using an HPLC/MS–MS after samples preparation. The excreted amounts of enantiomers in the urine showed a significant difference (P?<?0.05) except for 3–6?h. The cumulative excretion rate (Xu_0→24) in urine was 26.43?±?0.08% and 37.58?±?0.11% for R-(?)- and S-(+)-triticonazole, respectively, indicating high enantioselectivity (P?<?0.001). The cumulative excretion rate (Xu_0→72) in faeces was 6.93?±?0.03% and 6.77?±?0.03% for R-(?)- and S-(+)-triticonazole, respectively, without a difference. The results showed that the total cumulative percentage of triticonazole enantiomers accounted for in urine and faeces was 64.00?±?0.13% and 13.70?±?0.32%, the urinary excretion of R-(?)- and S-(+)-triticonazole were significantly different and S-(+)-triticonazole was preferentially excreted. However, the faecal excretion of the enantiomers showed no difference.     

Occurrence of free estrogens,conjugated estrogens,and bisphenol A in fresh livestock excreta and their removal by composting in North China

An efficient pretreatment and analytical method was developed to investigate the occurrence and fate of four free estrogens (estrone (E1), 17β-estradiol (17β-E2), estriol (E3), and 17α-ethinylestradiol (EE2)), four conjugated estrogens (estrone-3-sulfate sodium salt (E1-3S), 17β-estradiol-3-sulfate sodium salt (E2-3S), estrone-3-glucuronide sodium salt (E1-3G), and 17β-estradiol-3-glucuronide sodium salt (E2-3G)), and bisphenol A (BPA) in three livestock farms raising beef cattle, cows, sheep, swine, and chickens in Qi County, which is located in North China. The results demonstrated that one cow and one beef cattle excreted 956.25–1,270.41 and 244.38–319.99 μg/day of total (free and conjugated) estrogen, respectively, primarily through feces (greater than 91 %), while swine excreted 260.09–289.99 μg/day of estrogens, primarily through urine (98–99 %). The total estrogen excreted in sheep and broiler chicken feces was calculated to be 21.64–28.67 and 4.62–5.40 μg/day, respectively. It was determined that conjugated estrogens contributed to 21.1–21.9 % of the total estrogen excreted in cow feces and more than 98 % of the total estrogen excreted in swine urine. After composting, the concentration of total estrogen decreased by 18.7–59.6 %; however, increased levels of BPA were measured. In treated compost samples, estrogens were detected at concentrations up to 74.0 ng/g, which indicates a potential risk of estrogens entering the surrounding environment.     

Fate and availability of glyphosate and AMPA in agricultural soil

The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT(50) values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, (14)C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 +/- 0.002% and 0.005 +/- 0.001% of the applied radioactivity was measured in rape and barley, respectively.     

Occurrence and fate of polycyclic musks in wastewater treatment plants in Kentucky and Georgia, USA

Wastewater treatment plants (WWTPs) are a potential of source of polycyclic musks in the aquatic environment. In this study, contamination profiles and mass flow of polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[gamma]-2-benzopyran (HHCB), 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), and HHCB-lactone (oxidation product of HHCB), in two WWTPs, one located in Kentucky (Plant A, rural area) and the other in Georgia (Plant B, urban), USA, were determined. HHCB, AHTN and HHCB-lactone were detected in the influent, effluent, and sludge samples analyzed. The concentrations in wastewater samples varied widely, from 10 to 7,030 ng/l, 13 to 5,400 ng/l, and 66 to 790 ng/l, for HHCB, AHTN, and HHCB-lactone, respectively. Sludge samples contained HHCB at <0.02-36 microg/g dry weight, AHTN at <0.02-7.2 microg/g dry weight, and HHCB-lactone at <0.05-17 microg/g dry weight. Based on the daily flow rates and mean concentrations of polycyclic musks, the estimated discharge of total polycyclic musks to the rivers was 21 g/day from Plant A and 31 g/day from Plant B. Mass balance analysis suggested that only 30% of HHCB and AHTN entering the plants was accounted for in the effluent and the sludge. Removal efficiencies of HHCB and AHTN in the two WWTPs ranged from 72% to 98%. In contrast, HHCB-lactone concentrations increased following the treatment. Concentrations of polycyclic musks in sludge were on the order of several parts per million. Incineration of sludge at one plant reduced the concentration of polycyclic musks.     

PAHs composition of surface marine sediments: a comparison to potential local sources in Todos Santos Bay, B.C., Mexico

The analysis of the 16 polyaromatic hydrocarbons (PAHs) listed as priority pollutants by EPA, was carried out on surface sediments at 32 stations at Todos Santos Bay, Baja California, Mexico. The purpose was to investigate concentration levels, distribution patterns and relate them to three suspected local sources. The PAHs composition of car exhaust, grass and shrubs combustion, and asphalt and tire dust, were all compared to the relative abundance of PAHs signature found on marine sediments of the bay. We used GC-MS analysis in selected ion monitoring (SIM) mode. The total concentration found was low (from 7.6 to 813 ng/g of dry sediment. The average concentration was 96 ng/g). PAHs concentration was somewhat correlated (r = 0.612; P < 0.05) with organic matter content. Surface distributions suggest depositional patterns conforming to the reported water circulation in the bay. The maximum concentration was found near Todos Santos Canyon. The largest concentrations found were those of fluoranthene (120.6 ng/g), Indene(1,2,3-c,d)pyrene (115.6 ng/g) and pyrene (109.9 ng/g). Percentagewise, the main components were PAHs with three and four rings. Several indexes were used to investigate origins including simple PAH ratios and ternary plots. These indexes and plots suggest the main origin as a combination of urban air and wood and brush fires with little influence of oil.