Toxicity of a complex mixture of atmospherically transported pesticides to Ceriodaphnia dubia

The presence of several anthropogenic chemicals has been documented in the atmosphere of the Canadian prairies. The deposition of these chemicals as a mixture is of importancesince little is known of the combined effects of these chemicalson aquatic organisms. This study was designed to evaluate theacute and chronic toxicity of a complex mixture of nineatmospherically transported pesticides to Ceriodaphniadubia. The nine selected pesticides (bromoxynil, dicamba, 2,4-D,MCPA, triallate, trifluralin, pentachlorophenol, lindane, and4,4-DDT) were detected in appreciable quantities in dryatmospheric deposits. The concentration of each pesticide in themixture was based on maximum measured daily dry deposition ratesfor central Canada, except for pentachlorophenol, which wasestimated based on atmospheric concentrations. The 48-h LC50estimate for C. dubia exposed to the pesticide mixture was174.60 g L^-1 (340 times the measured total dry deposition concentration). The estimated NOEC and LOEC for bothsurvival and reproduction, as determined in the 7-d chronic toxicity test, were 51.3 (100 times) and 154 g L^-1 (300 times), respectively. A basic risk assessment, using the toxic unit approach, suggested that the toxicity of the pesticide mixture was mainly due to 4,4-DDT. Overall, this atmospherically transported complex mixture of pesticides appearsto pose a negligible toxicological risk to non-target aquatic invertebrates such as zooplankton.     

氟利昂替代品降解产物——三氟乙酸对水环境的潜在影响

三氟乙酸 (简称 TFA)是氟利昂替代品的主要降解产物之一 ,该物质会造成大气环境的恶化 ,雨水会将其从大气中去除。三氟乙酸化学性质极其稳定 ,在水中全部溶解。在自然条件下 ,三氟乙酸不降解、不光解、不被土壤吸附、不被微生物分解 ,易于在水体中积累 ,特别是在没有流入和流出的水体及季节性湿地中蓄积。全球雨水中的三氟乙酸 2 0 1 0年预计可达到 1 0 0～ 1 60 ng/L,部分地区地表水可达到 1 60 ng/L。     

31P-NMR evaluation of organophosphorus pesticides degradation through metal ion promoted hydrolysis

The degradation of some organophosphorus pesticides (OPPs) in the presence of metal ions was studied by ³¹P-NMR spectroscopy. Both ³¹P-NMR and gas chromatography/mass spectroscopy results were used in order to determine the nature of metabolites formed after degradation. The degraded organophosphorus pesticide were investigated for chlorpyrifos and phoxim in the presence of several metal ions including Hg²⁺, Cu²⁺, Cd²⁺, Ni²⁺, Pb²⁺, and Ag⁺. ³¹P-NMR results indicated Ag⁺ and Hg²⁺ ion promoted degradation of OPPs and other metal ions formed complex with OPPs and cannot degrade OPPs. We found that the degradation of chlorpyrifos and phoxim with Ag⁺ or Hg²⁺ led to the formation of O,O-diethyl-O-methyl phosphorothionate, (C₂H₅O)₂(CH₃O)PS, at metal ion/pesticide mole ratios ≤1.0 and completely decomposed at a higher mole ratio of 10. Finally, the method was successfully applied to the degradation study of a number of technical and formulated pesticides in the presence of Ag⁺ ion at a metal ion/pesticide mole ratio of 10.     

Tiered aquatic ecological risk assessment of organochlorine pesticides and their mixture in Jiangsu reach of Huaihe River, China

A tiered approach consisting of several probabilistic options was used to refine aquatic ecological risk assessment (ERA) of individuals and mixture of various Organochlorine Pesticides (OCPs) detected in Jiangsu reach of Huaihe River, China. The tiered approach ranged from determined Hazard Quotient (HQ) to Joint Probability Curve and Monte Carlo simulation based HQ-distribution. The results from all levels of ERA methods in the tiered framework are consistent with each other. The results show that Endrin, o,p'-Dichloro-Diphenyl-Trichloroethane (DDT), alpha-Endosulfan and beta-Endosulfan posed clear ecological risk; p,p'-DDT, p,p'-DDD, Aldrin, Heptachlorepoxide and Methoxychlor posed potential risk; while Hexachlorocyclohexanes, Heptachlor, Dieldrin and Hexachlorobenzene posed negligible risk. Further, based on the concept of total equivalent concentration, combined ecological risk caused by the mixture of all detected OCPs was calculated, and it proved to be significantly higher than the risk caused by any individual OCP. Despite inevitable uncertainties in current ERA, a comprehensive tiered approach can help to get a more credible result of risks of individuals and mixture of hazardous pollutants and screen the major risk pollutants contributing to the combined ecological risk.     

Community air monitoring for pesticides. Part 1: selecting pesticides and a community

The CA Department of Pesticide Regulation (CDPR) developed methods to select pesticides and a community to fulfill criteria for an ambient air monitoring study it conducted as part of the CA Environmental Protection Agency's Environmental Justice Action Plan. Using a scoring system, CDPR evaluated 100 pesticides based on statewide-reported pesticide use, volatility, and priority in CDPR's risk assessment process (indicators of exposure and toxicity) to produce a list of pesticides to consider as candidates for monitoring. The CDPR also evaluated and scored 83 communities based on demographics and health factors, availability of cumulative impacts data, and reported pesticide use to create a list of community candidates. The scores provide relative rankings to distinguish more highly impacted communities from less impacted ones and to identify which pesticides might contribute most to potential adverse health effects. These methods use criteria that can be quantified, validated, and verified in order to provide a transparent and fair selection process. Based on public comments and highest scores, CDPR recommended 40 pesticides (including some of their degradation products) and one community for its yearlong monitoring study. The CDPR then further refined its list of pesticides by soliciting input from local and technical advisory groups. The CDPR plans to use these methods to select pesticides and communities in future monitoring activities.     

The effects of pesticide mixtures on degradation of pendimethalin in soils

Most agronomic situations involve a sequence of herbicide, fungicide, and insecticide application. On the other hand, use of pesticidal combinations has become a standard practice in the production of many agricultural crops. One of the most important processes influencing the behavior of a pesticide in the environment is its degradation in soil. It is known that due to several pesticide applications in one vegetation season, the pesticide may be present in mixtures with other pesticides or xenobiotics in soil. This study examines the role which a mixture of chemicals plays in pesticide degradation. The influence of other pesticides on the rate of pendimethalin (PDM) degradation in soil was measured in controlled conditions. Mixtures of PDM with mancozeb or mancozeb and thiamethoxam significantly influenced the degradation of pendimethalin under controlled conditions. The second type of mixtures, with metribuzin or thiamethoxam, did not affect the behavior of pendimethalin in soil. Also, we determined the influence of water content on the rate of pendimethalin degradation alone in two soils and compared it to the rate in three pesticide mixtures. We compared two equations to evaluate the predictors of the rate of herbicide dissipation in soil: the first-order kinetic and the non-linear empirical models. We used the non-linear empirical model assuming that the degradation rate of a herbicide in soil is proportional to the difference of the observed concentration of herbicide in soil at time and concentration of herbicide in the last day of measurement.     

Bioaccumulation and related effects of PCBs and organochlorinated pesticides in freshwater fish Hypostomus commersoni

Few studies have investigated the bioaccumulation of persistent organic pollutants (POPs) in Brazilian native freshwater fish. In order to evaluate the bioavailability, potential risk to human exposure and the effects of POPs in the fish Hypostomus commersoni, muscle and liver samples of thirteen specimens were collected in a lake located in the city of Ponta Grossa (Parana State, Southern Brazil). Also, the liver and gills were considered for histopathological studies, and oxidative stress was investigated in the liver. Expressive concentrations of POPs were observed in the liver and muscle, with a total of 427 ± 78.7 and 69.2 ± 18.1 ng g(-1) dry weights of polychlorinated biphenyls (PCBs), respectively. Negative correlations between the concentration of several POPs and glutathione S-transferase and glucose-6-phosphate dehydrogenase were found. Otherwise, the cholinesterase activity in the muscle and brain presented positive correlations with the concentration of POPs. The hepatic bioaccumulation of some banned pesticides like aldrin, dieldrin and DDT was associated with various histopathological findings in the liver and gills. Necrotic areas, fibrosis, leukocyte infiltration, and the absence of macrophage centers were observed in the liver, indicating both chronic exposure and immunological suppression. Neoplasic changes were observed in the gills, confirming the carcinogenic potential reported for some of the investigated pollutants. The current work was the first to study the bioaccumulation of POPs in H. commersoni, an important species in ecological aspects and as a vehicle to human exposure to PCBs and organochlorine pesticides (OCPs).     

金属离子和氧化剂对3,5-二氯酚光化学降解的影响

在实验条件下 ,Fe2 +、KCl O3、KCl O4 、KBr O3、KIO4 对 3 ,5 -二氯酚光化学降解起加速作用 ,且随其浓度增大 ,加速作用也在增强。KIO4 的加速作用比较强。光照时 ,KIO4 +Mn2 +对 3 ,5 -二氯酚光化学降解的加速作用非常显著。无光照时 ,当 KMn O4 浓度增加时 ,3 ,5 -二氯酚被迅速氧化 ;KIO4 +Mn2 + /Fe2 + 能够使 3 ,5 -二氯酚发生化学降解 ,尤其是 KIO4 +Mn2 + 的作用。     

The effects assessment of firm environmental strategy and customer environmental conscious on green product development

The purpose of this study is to examine why both parties (industry and consumer market) have mutual interests in protecting the environment but they still are hesitant to act green. The study used two-stage sampling from consumer market to depict ideal green product characteristics and reliable toy companies, and visit these companies for the second sample collection to examine whether the organizational eco-innovation strategy with customer value has a positive effect on green product development. In other words, the customer's benefit is an important factor for new product development strategy for green toys. This research shows that the willingness to buy green toys increases if most people in society buy green toys. This represents that customers are environmentally conscious and care about protecting the environment, or buying green toys is the result of a new economic trend and childhood education. The willingness to buy green toys increases if customers think that green products implies an enhancement on new product development to toy manufacturers. Further, if manufacturers are able to manage the difficulty of cooperation with all parties in the supply chain and difficulties related to production, they are willing to adopt customers' perceived value on green toys for their new product development strategy. It is rare to find academic research discussing the perspectives of both consumers and manufacturers in the same study because the research topic is very broad and many conditions must be considered. This research aims to find the effect of consumer-perceived value and company eco-innovation on green product development.     

Impacts of pesticides in a Central California estuary

Recent and past studies have documented the prevalence of pyrethroid and organophosphate pesticides in urban and agricultural watersheds in California. While toxic concentrations of these pesticides have been found in freshwater systems, there has been little research into their impacts in marine receiving waters. Our study investigated pesticide impacts in the Santa Maria River estuary, which provides critical habitat to numerous aquatic, terrestrial, and avian species on the central California coast. Runoff from irrigated agriculture constitutes a significant portion of Santa Maria River flow during most of the year, and a number of studies have documented pesticide occurrence and biological impacts in this watershed. Our study extended into the Santa Maria watershed coastal zone and measured pesticide concentrations throughout the estuary, including the water column and sediments. Biological effects were measured at the organism and community levels. Results of this study suggest the Santa Maria River estuary is impacted by current-use pesticides. The majority of water samples were highly toxic to invertebrates (Ceriodaphnia dubia and Hyalella azteca), and chemistry evidence suggests toxicity was associated with the organophosphate pesticide chlorpyrifos, pyrethroid pesticides, or mixtures of both classes of pesticides. A high percentage of sediment samples were also toxic in this estuary, and sediment toxicity occurred when mixtures of chlorpyrifos and pyrethroid pesticides exceeded established toxicity thresholds. Based on a Relative Benthic Index, Santa Maria estuary stations where benthic macroinvertebrate communities were assessed were degraded. Impacts in the Santa Maria River estuary were likely due to the proximity of this system to Orcutt Creek, the tributary which accounts for most of the flow to the lower Santa Maria River. Water and sediment samples from Orcutt Creek were highly toxic to invertebrates due to mixtures of the same pesticides measured in the estuary. This study suggests that the same pyrethroid and organophosphate pesticides that have been shown to cause water and sediment toxicity in urban and agriculture water bodies throughout California, have the potential to affect estuarine habitats. The results establish baseline data in the Santa Maria River estuary to allow evaluation of ecosystem improvement as management initiatives to reduce pesticide runoff are implemented in this watershed.     

The effect of mixtures of organophosphate and carbamate pesticides on acetylcholinesterase and application of chemometrics to identify pesticides in mixtures

Organophosphate (OP) and carbamate (CP) pesticides act by the inhibition of acetylcholinesterase (AChE). This enables the use of this enzyme for the detection of these pesticides in the environment. While many studies have looked at the effect of single pesticides on AChE, the effect of mixtures of pesticides still requires extensive investigation. This is important to evaluate the cumulative risk in the case of simultaneous exposure to multiple pesticides. Therefore we examined the effect of five different pesticides (carbaryl, carbofuran, parathion, demeton-S-methyl, and aldicarb) on AChE activity to determine whether combinations had an additive, synergistic, or antagonistic inhibitory effect. Results indicated that the mixtures had an additive inhibitory effect on AChE activity. The data from the assays of the mixtures were used to develop and train an artificial neural network (ANN) which was then utilised successfully for the identification of pesticides and their concentrations in mixtures. This study is significant because it evaluated mixtures of OPs and CPs where previous studies focused on either OPs or CPs. Previous studies have only examined up to three pesticides while this study evaluated mixtures of five pesticides simultaneously. This is also the first study where an ANN was able to utilise data from the inhibition of a single enzyme to differentiate five different pesticides and their concentrations from mixtures.     

固相微萃取-毛细管气相色谱法快速同步分析水中有机氯及有机磷农药

固相微萃取是一种快速、简便,集萃取浓缩进样于一体的样品前处理技术,具有分析时间短、灵敏度高、无需有机溶剂的优点.用固相微萃取富集水中8种有机氯及7种有机磷农药,毛细管气相色谱ECD检测器分离分析,整个分析过程只需26min,检出限可达0.002～1μg/L,已用于地表水中有机氯及有机磷农药含量的测定.     

Assessing the effects of dam building on land degradation in central Iran with Landsat LST and LULC time series

This study aimed to analyze the impact of Zayandehrood Dam on desertification using the spatio-temporal dynamics of land use/land cover (LULC) and land surface temperature (LST) in an arid environment in central Iran from 1987 to 2014. The LULC and LST images were calculated from Landsat TM, ETM+, and OLI data, and their accuracies were assessed against reference data using error matrix and linear regression analysis. Results showed that salty and bare lands increased up to 57,302 ha, while agricultural lands declined substantially (28,275.58 ha) in the region. The changes in LULC classes resulted in dramatic variations in LST values. The average temperature showed a 5.03 °C increase, and the minimum temperature increased by 5.66 °C. LST had an increasing trend in bare lands (8.74 °C), poor rangelands (6.8 °C), agricultural lands (9.46 °C), salty lands (9.6 °C), and residential areas (3.18 °C) in this 27-year period. Rainfall and temperature trend analysis revealed that the main cause of these extreme changes in LULC and LST was largely attributed to the drying up of Zayandehrood River due to dam construction and allocating water mainly for industrial sectors. Results indicate that in addition to LULC changes, the spatio-temporal variations of LST can be used as an effective index in desertification assessment and monitoring in arid environments.     

Hydrology-linked spatial distribution of pesticides in a fjord system in Greenland

A pilot study is presented evaluating selected chlorinated pesticides as chemical tracers for water masses in a sub-Arctic fjord system (Godth?bsfjord, western Greenland). Polyoxymethylene (POM) based passive water samplers were deployed during summer-autumn 2010. The levels of the analysed chlorinated pesticides in the fjord surface waters were found to be low compared to earlier studies. α-Hexachlorocyclohexane (α-HCH) and hexachlorobenzene (HCB) were the predominant contaminants. However, these two compounds have higher levels in oceanic water compared to freshwater influenced fjord waters. These chemicals can thus be considered as indicators for direct atmospheric long-range transport, while the organochlorine pesticides like trans-, cis-chlordane, trans-nonachlor and oxychlordane that are detected in the inner parts of the fjord are indicators for potential freshwater sources such as rivers and glacial meltwater runoff (secondary sources). The average values were 50 pg L(-1) for HCB and 11 pg L(-1) for α-HCH. These concentrations are comparable to levels in fjords in Svalbard (Norwegian Arctic), but lower than in open and/or ice covered oceans in the Canadian Arctic. Two air samplers were deployed for the identification of direct atmospheric contributions. Local contamination sources do not contribute significantly. The study demonstrated the value of passive water sampling devices for comprehensive hydrological characterization of Arctic coastal waters.     

Impact of degradation on nitrogen transformation in a forest ecosystem of India

A study was performed selecting one protected forest and an adjacent degraded forest ecosystem to quantify the impact of forest degradation on soil inorganic nitrogen, fine root production, nitrification, N-mineralization and microbial biomass N. There were marked seasonal variations of all the parameters in the upper 0–10 and lower 10–20 cm depths. The seasonal trend of net nitrification and net N-mineralization was reverse of that for inorganic nitrogen and microbial biomass N. Net nitrification, net N-mineralization and fine root biomass values were highest in both forests during rainy season. On contrary, inorganic nitrogen and microbial biomass N were highest during summer season. There was a marked impact of forest degradation on inorganic nitrogen, fine root production nitrification, N-mineralization and microbial biomass observed. Soil properties also varied with soil depth. Fine root biomass, nitrification, N-mineralization and microbial biomass N decreased significantly in higher soil depth. Degradation causes decline in mean seasonal fine root biomass in upper layer and in lower depth by 37% and 27%, respectively. The mean seasonal net nitrification and N-mineralization in upper depth decreased by 42% and 37%, respectively and in lower depth by 42.21% and 39% respectively. Similarly microbial biomass N also decreased by 31.16% in upper layer 33.19% in lower layer.     

Organochlorine pesticides in the soil of a karst cave in Guilin, China

Organochlorine pesticides (OCPs) including HCH, DDT, chlordane, endosulfan, and endosulfan sulfate were analyzed in surface soil of the Dayan Cave to investigate their source and concentration levels in September 2006. Generally, the data showed that outside soil of the cave had much higher concentrations than inside soil for the most detected OCPs in the cave and both inside soil and outside soil showed much lower concentration levels (basically, the levels of OCPs were less than 0.7 ng/g) than those observed in other regions within and outside China other than TC (ranging from 3.22 to 5.00 ng/g) and CC (ranging from 3.89 to 5.08 ng/g) in the soil outside. The ratios of α-/γ-HCH ranged from 0.88 to 1.20 in the soil of the cave, together with the averaged percentages of β-HCH and δ-HCH among the total HCH isomers (accounting for 39.0% and 14.2%, respectively), implied that a historical residue of local technical HCH contamination was likely to be dominant in the soil of the cave. Based on (1) the accordance of TC/CC ratios (ranging from 0.83 to 0.98) between the values observed in the outside soil and the potentially available chlordane products in the markets, and (2) the high concentrations of TC and CC observed in the outside soil, it appeared that the illegal usage of technical chlordane was done in Guilin. The low concentrations of TC (0.02 to 0.56 ng/g) and CC (0.10 to 1.71 ng/g) in the inside soil, together with the significant distinctions of TC/CC ratios between the inside soil (ranging from 0.03 to 0.33) and the outside soil, implied that the chlordane in the inside soil of the cave was a historical residue of local technical chlordane contamination. The similar ratios of DDT isomers (o,?p (')-DDT/p,?p (')-DDT and p,?p (')-DDE+DDD/DDT) between the outside soil and the inside soil of the cave suggested that they may have the similar DDT source. The ratios of p,?p (')-DDE+DDD/DDT (ranging from 3 to 8) indicated that DDT was relatively aged. The values of o,?p (')-DDT/p,?p (')-DDT ratios (ranging from 3 to 7.5 with a mean value of 5.45) were found to be much higher than that of technical DDT, and very similar to that of dicofol products, implied that the primary source of DDT in the soil of the cave was most probably from dicofol-type DDT products. The low concentration levels of endosulfan and the higher levels of metabolite endosulfan sulfate indicated that the residue from historical usage of technical endosulfan was likely to be dominant in the soil of the cave.     

Polychlorinated biphenyls, organochlorine pesticides and polycyclic aromatic hydrocarbons in a one-off global survey of bivalves

During the Danish Galathea 3 expedition, bivalve samples were collected at the Faroe Islands, Greenland, Ghana, South Africa, Australia, Solomon Islands, New Zealand, Chile, US Virgin Islands, Boston, Newfoundland and Shetland Islands and analysed for organochlorines and PAHs. Concentration differences of up to three orders of magnitude were observed, with the highest concentrations at Boston harbour (SPCB 338 ng g(-1) dw, ΣSPAH 5966 ng g(-1) dw) and the Sydney estuary (ΣSPCB 282 ng g(-1) dw, SPAH 1453 ng g(-1) dw). Local impacts were also found for the Greenland capital Nuuk in terms of PCB and PAH levels, while other Greenland samples came closest to representing PAH background levels. Several locations had undetectable organochlorine levels, including Hobart and Chile, which had the lowest SPAH concentrations (<200 ng g(-1) dw). It was possible to group the stations according to their pyrogenic/petrogenic influence using Principal Component Analyses, and indications of petroleum sources were found at Nuuk.