Assessment of characteristic distribution of PCDD/Fs and BFRs in sludge generated at municipal and industrial wastewater treatment plants

The presence of polychlorinated dibenzo-p-dioxins and furan (PCDD/Fs) and brominated flame retardants (BFRs) in sludge generated at municipal wastewater treatment plants (MWTPs) and industrial wastewater treatment plants (IWTPs) was investigated. The concentrations of these pollutants were in the following ranges: 5.38-7947 ng kg⁻¹ dw (0.02-49.9 ng WHO-TEQ kg⁻¹ dw) for 17 PCDD/Fs, 17.5-66 761 μg kg⁻¹ dw for 27 polybrominated diphenyl ethers (PBDEs), 1.55-29 604 μg kg⁻¹ dw for hexabromocyclododecanes (HBCDs) (α-, β-, and γ-diastereomers), and 4.01-618 μg kg⁻¹ dw for tetrabromobisphenol A (TBBPA). Generally, the levels of each compound in the sewage-sludge samples were higher than those in the industrial-sludge samples with some exceptions. The characteristic distribution profiles of target compounds were observed for different types of sludge and different sources of wastewater. High-chlorinated PCDD/Fs were dominant in all samples except those from the textile industry. The distribution of the BFRs in industrial-sludge samples varied, whereas that of the BFRs in sewage-sludge samples was consistent. The proportion of penta-BDEs in sewage sludge was higher than that in industrial sludge, even though BDE-209 was the most dominant congener in all the samples. For HBCDs, the distribution of diastereomers (α-, β-, and γ-HBCD) was similar across sludge samples that had the same source of wastewater and treatment processes.     

Bioconcentration and depuration of endosulfan sulfate in mosquito fish (Gambusia affinis)

Endosulfan is an insecticide which has been widely used in agriculture. The technical grade material consists of two isomers (alpha and beta). Under natural environmental conditions, endosulfan is metabolized through oxidation and the main metabolite in the environment is endosulfan sulfate. Most ecotoxicology research has been conducted with technical grade endosulfan to determine effects on non-target aquatic organisms. Little data on the effects of endosulfan sulfate on aquatic organisms are available in the literature. This study characterizes endosulfan sulfate bioconcentration and depuration in mosquito fish (Gambusia affinis). During the study, G. affinis was exposed to an environmentally relevant endosulfan sulfate concentration of 0.25 μg L⁻¹ for 5 weeks (uptake phase) followed by a 3-week period (depuration phase) in clean water. This study found that G. affinis bioconcentrated endosulfan sulfate. During the exposure phase, fish tissue concentrations of endosulfan sulfate increased with time up to 730 μg kg⁻¹ dw or 215 μg kg⁻¹ ww. The bioconcentration data followed Michaelis-Menten kinetics better than the one-compartment first order kinetics (1-CFOK). Using these models, the bioconcentration factors for endosulfan sulfate-exposed G. affinis were from 687 to 888  L kg⁻¹ in wet weight or 2263 to 2936 L kg⁻¹ in dry weight. During the depuration phase, endosulfan sulfate concentrations in tissue significantly decreased and the data followed first order kinetics. The half-life of endosulfan sulfate in G. affinis was about 9 d. There was no significant difference in standard length or weight between control and exposed fish. The growth data followed the von Bertalanffy growth model. However, the condition factor of exposed fish increased with time during the exposure phase.     

Concentrations of cyclic volatile methylsiloxanes in biosolid amended soil,influent, effluent,receiving water,and sediment of wastewater treatment plants in Canada

A comprehensive surveillance program was conducted to determine the occurrence of three cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in environmental compartments impacted by wastewater effluent discharges. Eleven wastewater treatment plants (WWTPs), representative of those found in Southern Ontario and Southern Quebec, Canada, were investigated to determine levels of cVMS in their influents and effluents. In addition, receiving water and sediment impacted by WWTP effluents, and biosolid-amended soil from agricultural fields were also analyzed for a preliminary evaluation of the environmental exposure of cVMS in media impacted by wastewater effluent and solids. A newly-developed large volume injection (septumless head adapter and cooled injection system) gas chromatography – mass spectrometry method was used to avoid contamination originating from instrumental analysis. Concentrations of D4, D5, and D6 in influents to the 11 WWTPs were in the range 0.282–6.69 μg L⁻¹, 7.75–135 μg L⁻¹, and 1.53–26.9 μg L⁻¹, respectively. In general, wastewater treatment showed cVMS removal rates of greater than 92%, regardless of treatment type. The D4, D5, and D6 concentration ranges in effluent were <0.009–0.045 μg L⁻¹, <0.027–1.56 μg L⁻¹, and <0.022–0.093 μg L⁻¹, respectively. The concentrations in receiving water influenced by effluent, were lower compared to those in effluent in most cases, with the ranges <0.009–0.023 μg L⁻¹, <0.027–1.48 μg L⁻¹, and <0.022–0.151 μg L⁻¹ for D4, D5, and D6, respectively. Sediment concentrations ranged from <0.003–0.049 μg g⁻¹ dw, 0.011–5.84 μg g⁻¹ dw, and 0.004–0.371 μg g⁻¹ dw for D4, D5, and D6, respectively. The concentrations in biosolid-amended soil, having values of <0.008–0.017 μg g⁻¹ dw, <0.007–0.221 μg g⁻¹ dw, and <0.009–0.711 μg g⁻¹ dw for D4, D5, and D6, respectively, were lower than those in sediment impacted by wastewater effluent in most cases. In comparison with the no-observed-effected concentrations (NOEC) and IC50 (concentration that causes 50% inhibition of the response) values, the potential risks to aquatic, sediment-dwelling, and terrestrial organisms from these reported concentrations are low.     

Polycyclic aromatic hydrocarbons: bees, honey and pollen as sentinels for environmental chemical contaminants

Three beehive matrices, sampled in six different apiaries from West France, were analyzed for the presence of four polycyclic aromatic hydrocarbons (PAH4: benzo[a]pyrene, benzo[a]anthracene, benzo[b]fluoranthene and chrysene). Samples were collected during four different periods in both 2008 and 2009. Honey samples showed the lowest levels of PAH4 contamination (min = 0.03 μg kg⁻¹; max = 5.80 μg kg⁻¹; mean = 0.82 μg kg⁻¹; Sd = 1.17). Bee samples exhibited higher levels of PAH4 contamination (min = 0.32 μg kg⁻¹; max = 73.83 μg kg⁻¹; mean = 7.03 μg kg⁻¹; Sd = 17.83) with a great dispersion of the concentrations due to four main events of high concentrations. Pollen samples showed only one major episode with the highest PAH4 concentration found (min = 0.33 μg kg⁻¹; max = 129.41 μg kg⁻¹; mean = 7.10 μg kg⁻¹; Sd = 22.28). The PAH4 concentrations found were significantly influenced by the landscape context for all beehive samples.     

A human health risk assessment of rare earth elements in soil and vegetables from a mining area in Fujian Province,Southeast China

Contaminated food through dietary intake has become the main potential risk impacts on human health. This study investigated concentrations of rare earth elements (REEs) in soil, vegetables, human hair and blood, and assessed human health risk through vegetables consumption in the vicinity of a large-scale mining area located in Hetian Town of Changting County, Fujian Province, Southeast China. The results of the study included the following mean concentrations for total and bio-available REEs of 242.92 ± 68.98 (135.85–327.56) μg g⁻¹ and 118.59 ± 38.49 (57.89–158.96) μg g⁻¹ dry weight (dw) in agricultural soil, respectively, and total REEs of 3.58 ± 5.28 (0.07–64.42) μg g⁻¹ dw in vegetable samples. Concentrations of total REEs in blood and hair collected from the local residents ranged from 424.76 to 1274.80 μg L⁻¹ with an average of 689.74 ± 254.25 μg L⁻¹ and from 0.06 to 1.59 μg g⁻¹ with an average of 0.48 ± 0.59 μg g⁻¹ of the study, respectively. In addition, a significant correlation was observed between REEs in blood and corresponding soil samples (R² = 0.6556, p < 0.05), however there was no correlation between REEs in hair and corresponding soils (p > 0.05). Mean concentrations of REEs of 2.85 (0.59–10.24) μg L⁻¹ in well water from the local households was 53-fold than that in the drinking water of Fuzhou city (0.054 μg L⁻¹). The health risk assessment indicated that vegetable consumption would not result in exceeding the safe values of estimate daily intake (EDI) REEs (100−110 μg kg⁻¹ d⁻¹) for adults and children, but attention should be paid to monitoring human beings health in such rare earth mining areas due to long-term exposure to high dose REEs from food consumptions.     

Risk assessment of xenoestrogens in a typical domestic sewage-holding lake in China

Release of domestic sewage leads to accumulation of xenoestrogens in holding waters, especially in closed or semi-enclosed waters such as lakes. In the study, the occurrence, distribution, estrogenic activity and risk of eight xenoestreogens were evaluated in Lake Donghu, China. Nonylphenol (NP), octylphenol (OP), and bisphenol A (BPA) were identified as the main xenoestrogens ranging from tens of ng L⁻¹ (in the surface water) or ng g⁻¹ dw (in the suspended particles and sediment) to tens of μg L⁻¹ or μg g⁻¹ dw. The sum of 17β-estradiol equivalents (∑EEQs) ranged from 0.32 to 45.02 ng L⁻¹ in the surface water, 0.53 to 71.86 ng g⁻¹ dw in the suspended particles, and 0.09 to 24.73 ng g⁻¹ dw in the sediment. Diethylstilbestrol (DES) was determined as the main contributor to ∑EEQs followed by NP. The risk assessment showed a higher risk in the surface water than in the suspended particles and sediment in such domestic sewage-holding lake.     

Effect of land use change from paddy to vegetable field on the residues of organochlorine pesticides in soils

The effect of land use change from paddy to vegetable field on the residues of organochlorine pesticides (OCPs) was investigated. Soil residues of OCPs were analyzed in vegetable fields which had been converted from paddy fields for 0, 5, 10, 15, 20, 30, 50 year in Yixing, China in 2003. The mean concentrations of OCPs followed a sequence of: ∑DDTs (13.7 μg kg⁻¹) > ∑HCHs (8.6 μg kg⁻¹) > > HCB (2.09 μg kg⁻¹) > α-endosulfan (1.30 μg kg⁻¹) > endrin (1.08 μg kg⁻¹) > PCNB (0.76 μg kg⁻¹) > dieldrin (0.58 μg kg⁻¹). The mean residues of OCPs especially DDTs increased significantly with vegetable planting time after land use change in the first 15 years, then decreased from 20 to 30 years and increased a little afterward. The time under anaerobic and aerobic conditions was suggested to control mainly the change of the residues of OCPs.     

Relationships between hepatic trace element concentrations, reproductive status, and body condition of female greater scaup

We collected female greater scaup (Aythya marila) on the Yukon-Kuskokwim Delta, Alaska during two breeding seasons to determine if concentrations of 18 trace elements in livers and eggs were elevated and if hepatic concentrations correlated with body condition or affected reproductive status. Fifty-six percent, 5%, and 42% of females, respectively, had elevated hepatic cadmium (Cd: >3 μg g⁻¹ dry weight [dw]), mercury (Hg: >3 μg g⁻¹ dw), and selenium (Se: >10 μg g⁻¹ dw). Somatic protein and lipid reserves were not correlated with hepatic Cd or Hg, but there was a weak negative correlation between protein and Se. Hepatic Cd, Hg, and Se were similar in females that had and had not initiated egg production. In a sample of six eggs, 33% and 100%, respectively, contained Se and Hg, but concentrations were below embryotoxicity thresholds. We conclude that trace element concentrations documented likely were not adversely impacting this study population.     

Assessment of fates of estrogens in wastewater and sludge from various types of wastewater treatment plants

We measured five estrogens in the wastewater samples from the municipal wastewater treatment plants (M-WWTPs), livestock wastewater treatment plants (L-WWTPs), hospital WWTPs (H-WWTPs) and pharmaceutical manufacture WWTPs (P-WWTPs) in Korea. The L-WWTPs showed the highest total concentration (0.195-10.4 μg L⁻¹) of estrogens in the influents, followed by the M-WWTPs (0.028-1.15 μg L⁻¹), H-WWTPs (0.068-0.130 μg L⁻¹) and P-WWTPs (0.015-0.070 μg L⁻¹). Like the influents, the L-WWTPs (0.003-0.729 μg L⁻¹) and the M-WWTPs (0.001-0.299 μg L⁻¹) also showed higher total concentration of estrogens in the effluents than the H-WWTPs (0.002-0.021 μg L⁻¹) and P-WWTPs (0.011 μg L⁻¹ in one sample). The L-WWTPs (37.5-543 μg kg⁻¹, dry weight) showed higher total concentrations in sludge than the M-WWTPs (3.16-444 μg kg⁻¹, dry weight) like the wastewater. The distribution of estrogens in the WWTPs may be affected by their metabolism in the human body, their transition through biological treatment processes, and their usage for livestock growth. Unlike the concentration results, the daily loads of estrogens from the M-WWTPs were the highest, which is related to the high capacities of WWTPs.     

Occurrence and environmental implications of pharmaceuticals in Chinese municipal sewage sludge

The presence of pharmaceuticals in aquatic environment has become a topic of concern because of their potential adverse effects on human health and wildlife species. A total of 45 dewatered sewage sludge samples were collected throughout China and analyzed for 30 commonly consumed pharmaceutical residues. Ofloxacin was found to be the dominant contaminant with concentrations up to 24 760 μg kg⁻¹, followed by oxytetracycline (5280 μg kg⁻¹), norfloxacin (5280 μg kg⁻¹) and ketoprofen (4458 μg kg⁻¹). The concentration of pharmaceutical residues varied greatly depending on the operation conditions of wastewater treatment plants and sampling locations. Poor agreement was found between the predicted (calculation based on the annual consumption and coefficient of sludge water partition) and detected concentrations of the pharmaceuticals indicating that the occurrence of pharmaceutical residues was affected by various factors such as loading rates, sewage properties and the chemical properties such as the contribution from polar groups. National wide fate and ecotoxicity study is required for the development of control strategies.     

Formation of dioxins during exposure of pesticide formulations to sunlight

Chlorinated pesticides can contain impurities of dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and their precursors, as a result of various manufacturing processes and conditions. As precursor formation of PCDD/Fs can also be mediated by ultraviolet light (UV), this study investigated whether PCDD/Fs are formed when currently used pesticides are exposed to natural sunlight. Formulations containing pentachloronitrobenzene (PCNB; n = 2) and 2,4-dichlorophenoxyacetic acid (2,4-D; n = 1) were exposed to sunlight in quartz tubes, and the concentration of 93 PCDD/F congeners were monitored over time. Considerable formation of PCDD/Fs was observed in both PCNB formulations (by up to 5600%, to a maximum concentration of 57 000 μg ∑PCDD/F kg⁻¹) as well as the 2,4-D formulation (by 3000%, to 140 μg ∑PCDD/F kg⁻¹). TEQ also increased by up to 980%, to a maximum concentration of 28 μg kg⁻¹ in PCNB, but did not change in the 2,4-D formulation. Assuming similar yields as observed in the present study as a worst case scenario the use of PCNB in Australia may result in the formation of 155 g TEQ annum⁻¹, contributed primarily by OCDD formation. This warrants detailed evaluations on the contemporary release of PCDD/Fs to the environment after the use of pesticides. Changes in congener profiles (including the ratio of PCDDs to PCDFs (DF ratio)) suggest that pesticide sources of PCDD/Fs after sunlight exposure may not be recognized based on matching source fingerprints established from manufacturing impurities. These changes also provide preliminary insights into the possible formation routes and types of precursors involved.     

Occurrence of antibiotics in water, sediments, aquatic plants, and animals from Baiyangdian Lake in North China

This study investigated the presence and distribution of 22 antibiotics, including eight quinolones, nine sulfonamides and five macrolides, in the water, sediments, and biota samples from Baiyangdian Lake, China. A total of 132 samples were collected in 2008 and 2010, and laboratory analyses revealed that antibiotics were widely distributed in the lake. Sulfonamides were the dominant antibiotics in the water (0.86-1563 ng L⁻¹), while quinolones were prominent in sediments (65.5-1166 μg kg⁻¹) and aquatic plants (8.37-6532 μg kg⁻¹). Quinolones (17.8-167 μg kg⁻¹) and macrolides [from below detection limit (BDL) to 182 μg kg⁻¹] were often found in aquatic animals and birds. Salvinia natans exhibited the highest bioaccumulation capability for quinolones among three species of aquatic plants. Geographical differences of antibiotic concentrations were greatly due to anthropogenic activities. Sewage discharged from Baoding City was likely the main source of antibiotics in the lake. Risk assessment of antibiotics on aquatic organisms suggested that algae and aquatic plants might be at risk in surface water, while animals were likely not at risk.     

The influence of mariculture on mercury distribution in sediments and fish around Hong Kong and adjacent mainland China waters

To study the influence of mariculture on mercury (Hg) speciation and distribution in sediments and cultured fish around Hong Kong and adjacent mainland China waters, sediment samples were collected from six mariculture sites and the corresponding reference sites, 200-300 m away from the mariculture sites. Mariculture activities increased total mercury, organic matter, carbon, nitrogen and sulfur concentrations in the surface sediments underneath mariculture sites, possibly due to the accumulation of unconsumed fish feed and fish excretion. However, methylmercury (MeHg) concentrations and the ratio of MeHg to THg (% MeHg) in sediments underneath mariculture sites were lower than the corresponding reference sites. The % MeHg in sediments was negatively correlated (r = −0.579, p < 0.05) with organic matter (OM) content among all sites, indicating that OM may have inhibited Hg methylation in surface sediments. Three mariculture fish species were collected from each mariculture site, including red snapper (Lutjanus campechanus), orange-spotted grouper (Epinephelus coioides) and snubnose pompano (Trachinotus blochii). The average MeHg concentration in fish muscle was 75 μg kg⁻¹ (wet weight), and the dietary intake of MeHg through fish consumption for Hong Kong residents was 0.37 μg kg⁻¹ week⁻¹, which was lower than the corresponding WHO limits (500 μg kg⁻¹ and 1.6 μg kg⁻¹ week⁻¹).     

Organ-wise accumulation of fluoride in Prosopis juliflora and its potential for phytoremediation of fluoride contaminated soil

Fluoride (F) contamination is a global environmental problem, as there is no cure of fluorosis available yet. Prosopis juliflora is a leguminous perennial, phreatophyte tree, widely distributed in arid and semi-arid regions of world. It extensively grows in F endemic areas of Rajasthan (India) and has been known as a “green” solution to decontaminate cadmium, chromium and copper contaminated soils. This study aims to check the tolerance potential of P. juliflora to accumulate fluoride. For this work, P. juliflora seedlings were grown for 75 d on soilrite under five different concentrations of F viz., control, 25, 50, 75 and 100 mg NaF kg⁻¹. Organ-wise accumulation of F, bioaccumulation factor (BF), translocation factor (TF), growth ratio (GR) and F tolerance index (TI) were examined. Plant accumulated high amounts of F in roots. The organ-wise distribution showed an accumulation 4.41 mg kg⁻¹dw, 12.97 mg kg⁻¹dw and 16.75 mg kg⁻¹dw F, in stem, leaves and roots respectively. The results indicated significant translocation of F from root into aerial parts. The bioaccumulation and translocation factor values (>1.0) showed high accumulation efficiency and tolerance of P. juliflora to F. It is concluded that P. juliflora is a suitable candidate for phytoremediation purpose and can be explored further for the decontamination of F polluted soils.     

Aluminum water treatment residuals as permeable reactive barrier sorbents to reduce phosphorus losses

Two aluminum water treatment residuals (Al-WTRs) from water treatment plants in Manatee County, FL and Punta Gorda, FL were evaluated as potential permeable reactive barrier (PRB) media to reduce groundwater phosphorus (P) losses. Short-term (<24 h) P sorption kinetics and long-term P sorption capacity were determined using batch equilibration studies. Phosphorus desorption was characterized following P loadings of 10, 20, 30, 40 and >70 g kg⁻¹. Sorption and desorption studies were conducted on the <2.0 mm material and three size fractions within the <2.0 mm material. The effect of dissolved organic carbon (DOC) on P retention was determined by reacting Al-WTRs with P-spiked groundwater samples of varying initial DOC concentrations. Phosphorus sorption kinetics were rapid for all size fractions of both Al-WTRs (>98% P sorption effectiveness at shaking times ?2 h). The effect of DOC was minimal at <150 mg DOC L⁻¹, but modest reductions (<22%) in P sorption effectiveness occurred at 587 mg DOC L⁻¹. The P sorption capacities of the Manatee and Punta Gorda Al-WTRs (<2.0 mm) are ∼44 g kg⁻¹ and >75 g kg⁻¹, respectively, and the lifespan of an Al-WTR PRB is likely many decades. Desorption was minimal (<2% of the P sorbed) for cumulative P loadings <40 g kg^-l, but increased (<9% of the P sorbed) at cumulative P loads >70 g kg⁻¹. The <2.0 mm Manatee and Punta Gorda Al-WTRs are regarded as ideal PRB media for P remediation.     

Immunotoxicity in ascidians: antifouling compounds alternative to organotins: III--the case of copper(I) and Irgarol 1051

After the widespread ban of TBT, due to its severe impact on coastal biocoenoses, mainly related to its immunosuppressive effects on both invertebrates and vertebrates, alternative biocides such as Cu(I) salts and the triazine Irgarol 1051, the latter previously used in agriculture as a herbicide, have been massively introduced in combined formulations for antifouling paints against a wide spectrum of fouling organisms. Using short-term (60 min) haemocyte cultures of the colonial ascidian Botryllus schlosseri exposed to various sublethal concentrations of copper(I) chloride (LC₅₀ = 281 μM, i.e., 17.8 mg Cu L⁻¹) and Irgarol 1051 (LC₅₀ > 500 μM, i.e., >127 mg L⁻¹), we evaluated their immunotoxic effects through a series of cytochemical assays previously used for organotin compounds. Both compounds can induce dose-dependent immunosuppression, acting on different cellular targets and altering many activities of immunocytes but, unlike TBT, did not have significant effects on cell morphology. Generally, Cu(I) appeared to be more toxic than Irgarol 1051: it significantly (p < 0.05) inhibited yeast phagocytosis at 0.1 μM (∼10 μg L⁻¹), and affected calcium homeostasis and mitochondrial cytochrome-c oxidase activity at 0.01 μM (∼1 μg L⁻¹). Both substances were able to change membrane permeability, induce apoptosis from concentrations of 0.1 μM (∼10 μg L⁻¹) and 200 μM (∼50 mg L⁻¹) for Cu(I) and Irgarol 1051, respectively, and alter the activity of hydrolases. Both Cu(I) and Irgarol 1051 inhibited the activity of phenoloxidase, but did not show any interactive effect when co-present in the exposure medium, suggesting different mechanisms of action.     

Organochlorine pesticide residues in sediments from the Uganda side of Lake Victoria

Organochlorine (OC) residues were analysed in 117 sediment samples collected from four bays of the Uganda side of Lake Victoria. The sediments were collected with a corer at a depth of 0-20 cm, and extracted for OC residues using a solid dispersion method. The extracts were cleaned using gel permeation chromatography and analysed for pesticide residues using a gas chromatograph (GC) equipped with an electron capture detector. The results were confirmed using a GC equipped with a mass spectrometer (MS). A total of 16 OC residues, most of them persistent organic pollutants (POPs) were identified and quantified. The OC residue levels were expressed on an oven dry weight (d.w.) basis. Endosulphan sulphate, in the range of 0.82-5.62 μg kg⁻¹d.w., was the most frequently detected residue. Aldrin and dieldrin were in the ranges of 0.22-15.96 and 0.94-7.18 μg kg⁻¹d.w., respectively. DDT and its metabolites lay between 0.11-3.59 for p,p′-DDE, 0.38-4.02 for p,p′-DDD, 0.04-1.46 for p,p′-DDT, 0.07-2.72 for o,p′-DDE and 0.01-1.63 μg kg⁻¹d.w. for o,p′-DDT. The levels of γ-HCH varied from 0.05 to 5.48 μg kg⁻¹d.w. Heptachlor was detected only once at a level of 0.81 μg kg⁻¹d.w., while its photo-oxidation product, heptachlor epoxide, ranged between non-detectable (ND) to 3.19 μg kg⁻¹d.w. Chlordane ranged from ND to 0.76 μg kg⁻¹d.w. Based on the threshold effect concentration (TEC) for fresh water ecosystems, aldrin and dieldrin were the only OCs that seemed to be a threat to the lake environment.     

Endosulfan induces changes in spontaneous swimming activity and acetylcholinesterase activity of Jenynsia multidentata (Anablepidae, Cyprinodontiformes)

We assessed changes in spontaneous swimming activity and acetylcholinesterase (AchE) activity of Jenynsia multidentata exposed to Endosulfan (EDS). Females of J. multidentata were exposed to 0.072 and 1.4 μg L⁻¹ EDS. Average speed and movement percentage were recorded during 48 h. We also exposed females to EDS at five concentrations between 0.072 and 1.4 μg L⁻¹ during 24 h, and measured the AchE activity in brain and muscle. At 0.072 μg L⁻¹ EDS swimming motility decreased relative to the control group after 45 h, while at 1.4 μg L⁻¹ EDS swimming motility decreased after 24 h. AchE activity significantly decreased in muscle when J. multidentata were exposed to EDS above 0.072 μg L⁻¹, while no significant changes were observed in brain. Thus, changes in swimming activity and AchE activity in muscle are good biomarkers of exposure to EDS in J. multidentata.     

Biological monitoring of chlorpyrifos exposure to rice farmers in Vietnam

Chlorpyrifos is the most common organophosphate insecticide registered for use in Vietnam and is widely used in agriculture, particularly rice farming. However, chlorpyrifos exposure to and adverse effects on farmers has not been evaluated. In this study, biological monitoring of chlorpyrifos exposure in a group of rice farmers was conducted after a typical application event using back-pack spraying.Urine samples (24 h) were collected from the rice farmers before and post insecticide application. Samples were analysed for 3,5,6-trichloropyridinol (TCP), the major urinary metabolite of chlorpyrifos, using an enzymatic pre-treatment before extraction followed by HPLC-MS/MS. Absorbed Daily Dose (ADD) of chlorpyrifos for farmers were then estimated from urinary TCP levels, expressed as μg g⁻¹ creatinine. The analytical method for urinary TCP had a low detection limit (0.6 μg L⁻¹), acceptable recovery values (80-114%), and low relative percentage differences in duplicate and repeated samples.Post-application chlorpyrifos ADD of farmers varied from 0.4 to 94.2 μg kg⁻¹ (body weight) d⁻¹ with a mean of 19.4 μg kg⁻¹ d⁻¹ which was approximately 80-fold higher than the mean baseline exposure level (0.24 μg kg⁻¹ d⁻¹). Hazard Quotients (ratio of the mean ADD for rice farmers to acute oral reference dose) calculated using acute oral reference doses recommended by United States and Australian agencies varied from 2.1 (Australian NRA), 4.2 (US EPA) to 6.9 (ATSDR).Biological monitoring using HPLC-MS/MS analysis of urinary TCP (24 h) was found to be an effective method for measuring chlorpyrifos exposure among farmers. This case study found that Vietnamese rice farmers had relatively high exposures to chlorpyrifos after application, which were likely to have adverse health effects.     

Long-term records of cadmium and silver contamination in sediments and oysters from the Gironde fluvial-estuarine continuum - evidence of changing silver sources

The Gironde fluvial estuarine system is impacted by historic metal pollution (e.g. Cd, Zn, Hg) and oysters (Crassostrea gigas) from the estuary mouth have shown extremely high Cd concentrations for decades. Based on recent work (Chiffoleau et al., 2005) revealing anomalously high Ag concentrations (up to 65 mg kg⁻¹; dry weight) in Gironde oysters, we compared long-term (∼1955-2001) records of Ag and Cd concentrations in reservoir sediment with the respective concentrations in oysters collected between 1979 and 2010 to identify the origin and historical trend of the recently discovered Ag anomaly. Sediment cores from two reservoirs upstream and downstream from the main metal pollution source provided information on (i) geochemical background (upstream; Ag: ∼0.3 mg kg⁻¹; Cd: ∼0.8 mg kg⁻¹) and (ii) historical trends in Ag and Cd pollution. The results showed parallel concentration-depth profiles of Ag and Cd supporting a common source and transport. Decreasing concentrations since 1986 (Cd: from 300 to 11 mg kg⁻¹; Ag: from 6.7 to 0.43 mg kg⁻¹) reflected the termination of Zn ore treatment in the Decazeville basin followed by remediation actions. Accordingly, Cd concentrations in oysters decreased after 1988 (from 109 to 26 mg kg⁻¹, dry weight (dw)), while Ag bioaccumulation increased from 38 up to 116 mg kg⁻¹, dw after 1993. Based on the Cd/Ag ratio (Cd/Ag ∼ 2) in oysters sampled before the termination of zinc ore treatment (1981-1985) and assuming that nearly all Cd in oysters originated from the metal point source, we estimated the respective contribution of Ag from this source to Ag concentrations in oysters. The evolution over the past 30 years clearly suggested that the recent, unexplained Ag concentrations in oysters are due to increasing contributions (>70% after 1999) by other sources, such as photography, electronics and emerging Ag applications/materials.