Integration of long-term fish kill data with ambient water quality monitoring data and application to water quality management

Almost half (354) of all fish kills (805) in South Carolina, USA, between 1978 and 1988 occurred in the coastal zone. These kills were analyzed for causative, spatial, and temporal associations as a distinct data set and as one integrated with ambient water quality monitoring data. Estuarine kills as a result of natural causes accounted for 42.8% followed by man-induced (35.1%) and undetermined causes (22.1%). Although general pesticide usage was responsible for 53.9% of man-induced kills, weed control activities around resorts and municipal areas accounted for slightly more kills (20.9%) than did agricultural (19.8%) or vector control (13.2%) uses. A dramatic decline in agricultural-related kills has been observed since 1986 as the integrated pest management approach was adopted by many farmers. When taken with the few kills (12.0%) resulting from wastewaters, this suggests that these two land-use activities have been successfully managed via existing programs (IPM and NPDES, respectively) to minimize their contributions to estuarine fish kills. Ambient trend monitoring data demonstrated no coastal-wide dispersion of pesticide pollution. These data confirmed the nature of fish kills to be site-specific, near-field events most closely associated with the contiguous land-use practices and intensities. Typically, fish kill data are considered as event-specific data limited to the bounds of that event only. Our analysis has shown, however, that a long-term data set, when integrated with ambient water quality data, can assist in regulatory and resource management decisions for both short- and long-term planning and protection applications.     

Wellhead treatment costs for groundwater contaminated with pesticides: A preliminary analysis for pineapple in Hawaii

In Hawaii, trace concentrations of pesticides used in the production of pineapple were found in the groundwater supplies of Mililani Town in the Pearl Harbor Basin on the island of Oahu. Groundwater serves as the major source of drinking water and residents pay for wellhead treatment of the contaminated water, via their monthly water bill. The agricultural chemical users within the Pearl Harbor Basin do not include these wellhead treatment costs in their production costs. The agricultural industry benefits from using pesticides but does not pay the entire societal cost of using these chemicals. In this study we evaluate the specific financial cost of wellhead treatment, and not the economic value of groundwater. While wellhead treatment costs could conceivably be shared by several parties, this study focuses on the financial impact of the pineapple industry alone. This study factors annual wellhead treatment costs into annual pineapple production costs to measure the effect on annual financial return from pineapple production. Wellhead treatment costs are calculated from the existing granulated activated carbon (GAC) water treatment facility for Millilani Wells I and II. Pineapple production costs are estimated from previous cost of production studies. The inclusion of wellhead treatment costs produces different production-cost results, depending on the scale of analysis. At the local scale, the Mililani wellhead treatment costs can be factored into the production costs of the pineapple fields, which were probably responsible for contamination of the Mililani Wells, without causing a deficit in economic return. At the larger regional scale, however, the return from all of the pineapple grown in the Pearl Harbor Basin can not sustain the cost of wellhead treatmentfor the entire water supply of the basin. Recommendations point to the prevention of groundwater contamination as more cost-effective measure than wellhead treatment.     

POLLUTIONAL ASPECTS OF PESTICIDES IN NATURAL STREAMS

The extensive use of synthetic organic pesticides in this country during the past twenty-five years has resulted in widespread pollution of our water resources. An obvious detrimental effect of such pollution has been observed in the numerous fish kills that have occurred. The most widely used pesticides, and the ones that have been implicated in the vast majority of the pollutional episodes, are the chlorinated hydrocarbon insecticides. These compounds, generally speaking, have almost no solubility in water, are subject to very slow microbial degradation if any at all, and are so resistent to natural degradation forces they can persist almost indefinitely in aqueous environments; characteristics that are all detrimental from a stream pollution standpoint. In addition, studies have shown that, as a group, the chlorinated hydrocarbons are more toxic to higher forms of aquatic life than other chemicals widely used for pest control. Because of these undesirable characteristics, present trends are to discontinue using these highly toxic, persistent compounds for pest control in outdoor areas. Legislation banning the sale of DDT has been introduced. Similar legislation controlling the use of several of the chlorinated hydrocarbon pesticides is probably the most effective way to reduce pollution.     

Predicting the aquatic risk of realistic pesticide mixtures to species assemblages in Portuguese river basins

Although pesticide regulatory tools are mainly based on individual substances, aquatic ecosystems are usually exposed to multiple pesticides from their use on the variety of crops within the catchment of a river. This study estimated the impact of measured pesticide mixtures in surface waters from 2002 and 2008 within three important Portuguese river basins (‘Mondego’, ‘Sado’ and ‘Tejo’) on primary producers, arthropods and fish by toxic pressure calculation. Species sensitivity distributions (SSDs), in combination with mixture toxicity models, were applied. Considering the differences in the responses of the taxonomic groups as well as in the pesticide exposures that these organisms experience, variable acute multi-substance potentially affected fractions (msPAFs) were obtained. The median msPAF for primary producers and arthropods in surface waters of all river basins exceeded 5%, the cut-off value used in the prospective SSD approach for deriving individual environmental quality standards. A ranking procedure identified various photosystem II inhibiting herbicides, with oxadiazon having the relatively largest toxic effects on primary producers, while the organophosphorus insecticides, chlorfenvinphos and chlorpyrifos, and the organochloride endosulfan had the largest effects on arthropods and fish, respectively. These results ensure compliance with European legislation with regard to ecological risk assessment and management of pesticides in surface waters.     

Sorption of Pesticides on Kaolinite and Montmorillonite as a Function of Hydrophilicity

Pesticides and other organic species are adsorbed by soil via different mechanisms, with bond strengths that depend on the properties of both the soil and the pesticide. Since the clay fraction in soil is a preferential sorbent for organic matter, reference kaolinite and montmorillonite are useful models for studying the mechanism and the strength of sorption. This paper presents the results of batch experiments to investigate the interactions of kaolinite KGa-1 and montmorillonite SWy-1 with the following pesticides and organic species resulting from the natural degradation of pesticides in the environment: atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine), diuron [1,1-dimethyl-3-(3,4-dichlorophenyl)urea], aniline, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Each of these chemicals has different hydrophilicity. Systems containing 2.0 g of clay were put in contact with 100.0 mL of solutions of the pesticides at known concentration ranging from 1.0 to 5.0 mg/L, and the amount of solute adsorbed was evaluated through RP-HPLC analysis of the pesticide still present in the aqueous suspension. To test for electrostatic interactions between the clay surface and the pesticides, potentiometric titration was used to determine the permanent surface charge of clays. Experiments were performed at different pH values. The results indicate that, for the chemicals studied, neutral molecules are preferentially retained relative to ionized ones, and that montmorillonite is a more effective sorbent than kaolinite.     

Investigation of various physicochemical and environmental parameter influence on pesticide sorption to ditch bed substratum by means of experimental design

Diffuse pollution by pesticide applied in rural catchments may contribute to alter water quality. Besides actions relative to the way the substances are introduced into the environment, it is also possible to limit the contamination by interfering on their transfer pathways from fields to the main river network. Especially, interface areas such as buffer strips or small ditches may play a major part in pesticide diffuse pollution decrease. In ditches a great variety of materials may act as sorbents for organic contaminants: grass, leaves, wood debris or sediments. In this study, laboratory experiments were designed to determine sorption characteristics for three herbicides with different physicochemical properties on sediment and leaves in decay commonly found in agricultural ditches. Sorption capacities were assessed for the herbicides isoproturon, diuron and diflufenican.

Experimental design was carried out to investigate the effects of five parameters on herbicide sorption on sediment and dead leaves. These parameters have been chosen according to parallel field experiment needs. Thus, the influence of initial sorbent moisture, herbicide form, i.e. active substance or commercial formulation, water quality (tap or natural ditch water), bromide ions (used as conservative tracers) and solid/liquid ratio have been tested. Within the parameters investigated, pesticide formulation and solid/liquid ratio were the most important parameters affecting pesticide sorption on both ditch materials.     

The use of nanovermiculite catalyst in the study of removal of the organic load and degradation of atrazine via ozone process in RPB reactor

Abstract

The main objective of this study is the degradation of a synthetic solution of atrazine by a modified vermiculite catalyzed ozonation, in a rotating packed bed (RPB) reactor. A 0.5?L RPB reactor was used to perform the experiments, using a Central Composite Design (CCD) response surface to construct the quadratic model based on the factors: pH, catalyst concentration and reactor rotation frequency. The response variable was the removal of the organic load measured in terms of Chemical Oxygen Demand (COD). After the complete quadratic model was constructed through the response surface, the COD degradation process had an optimal removal of 41% under the following conditions: pH 8.0, rotation of 1150?rpm and catalyst concentration 0.66?g L^?1.     

农药废水中有机硫、磷污染物湿式空气氧化反应的研究

以o,o-二甲氧基或o,o-二乙氧基硫代磷酰氯废水为典型废水,在180—230℃,氧气压力为0.7—1.5MPa的反应条件下,在2L的不锈钢高压釜中,研究了农药废水中有机硫磷化合物在湿式空气氧化过程中的降解机制。实验结果表明,有机硫磷化合物分子中的有机硫通过氧化反应降解为硫酸,有机磷通过水解反应降解为磷酸。有机硫氧化生成的硫酸是废水湿式空气氧化过程中酸度增加的主要来源,酸性条件比碱性条件更利于有机硫磷化合物的湿式空气氧化降解。     

Using the expert model PERPEST to translate measured and predicted pesticide exposure data into ecological risks

An important topic in the registration of pesticides and the interpretation of monitoring data is the estimation of the consequences of a certain concentration of a pesticide for the ecology of aquatic ecosystems. Solving these problems requires predictions of the expected response of the ecosystem to chemical stress. Up until now, a dominant approach to come up with such a prediction is the use of simulation models or safety factors. The disadvantage of the use of safety factors is a crude method that does not provide any insight into the concentration–response relationships at the ecosystem level. On the other hand, simulation models also have serious drawbacks like that they are often very complex, lack transparency, their implementation is expensive and there may be a compilation of errors, due to uncertainties in parameters and processes. In this paper, we present the expert model prediction of the ecological risks of pesticides (PERPEST) that overcomes these problems. It predicts the effects of a given concentration of a pesticide based on the outcome of already performed experiments using experimental ecosystems. This has the great advantage that the outcome is more realistic. The paper especially discusses how this model can be used to translate measured and predicted concentrations of pesticides into ecological risks, by taking data on measured and predicted concentrations of atrazine as an example. It is argued that this model can be of great use to evaluate the outcome of chemical monitoring programmes (e.g. performed in the light of the Water Framework Directive) and can even be used to evaluate the effects of mixtures.     

Remediation of s-triazines contaminated water in a laboratory scale apparatus using zero-valent iron powder

Atrazine, propazine and simazine were tested separately and in mixture by batch procedure in a laboratory-constructed apparatus. 3.75 l of a buffered s-triazines pesticide solution was treated at room temperature by 325-mesh zero-valent iron powder (ZVIP) (20 g/l). High performance liquid chromatography was used to separate by-products and study the decline in the pesticide’s concentrations. Results obtained show that the order of degradation was simazine, atrazine and then propazine. The half-lives (t_1/2) of the s-triazines pesticides are, respectively, 7.4, 9.0 and 10.6 min when they are treated separately, and 9.8, 11.2 and 13.7 min when they are treated together under the same conditions. The final by-product obtained after 50 min of contact of simazine with ZVIP shows a shift to longer wavelength in its UV spectrum. A similar phenomenon is shown for atrazine and propazine. Identical primary by-products are produced and subsequently degraded to 4,6-(diamino)-s-triazine, which seems to be the major by-product of the reductive treatment process. Pathways for the degradation of the studied s-triazines by ZVIP are proposed.