Solid‐phase extraction and GC analyses of select agricultural pesticides and metabolites in stream water

Abstract

The occurrence of agricultural pesticides in surface waters around the USA has created a concern over the status of safe drinking water. Solid‐phase extraction (SPE) or liquid‐liquid extraction (LLE) is usually employed to concentrate trace levels of pesticides in water samples to concentrations that are measurable with advanced chromatographic instruments. We describe here a SPE and capillary gas chromatographic (GC) procedure to extract and concentrate trace levels of select agricultural pesticides and metabolites from stream water. Our SPE and GC method provides high sensitivity, with recoveries between 85% to 95%, and high reproducibility for 9 of the pesticides studied. The described method provided marginal recoveries of 19 and 60% for the atrazine metabolites.     

Volatilization of lindane from water in soil‐free and flooded soil systems

Abstract

Volatilization of ¹⁴C‐lindane from water in planchets and under flooded soil ecosystem was investigated. Lindane disappeared faster than parathion from planchets. More rapid loss of both insecticides occurred from water than from chloroform. Loss of lindane and parathion was related to measured losses of water by evaporation. During 5‐day incubation under flooded soil conditions, disappearance of lindane was faster from open vials than from sealed vials, whereas in nonflooded soil, no volatile loss of the insecticide was evident despite water evaporation. Over 5 day incubation under flooded conditions, greater volatile loss of lindane occurred in sandy soil than in alluvial soil apparently due to greater adsorption to the soil colloids decreasing the insecticide concentration in the standing water of the laterite soil. Under identical conditions of water evaporation, lindane loss was directly proportional to its initial concentration in the water. These results suggest that considerable loss of soil applied pesticides can occur by volatilization from the standing water in flooded rice fields, particularly under tropical conditions.     

An overview of short‐term tests for the mutagenic and carcinogenic potential of pesticides

Abstract

In the last few years, marked progress has been made in the development of methods for evaluating the mutagenic and carcinogenic potential of pesticide chemicals. The correlation of genetic and related biological activity in short‐term tests with carcinogenic activity in whole animals allows the utilization of short‐term mutagenicity bioassays to prescreen chemicals for effects related to mutation induction and presumptive carcinogenicity. In addition, bioassays now available can measure directly the chemical transformation of normal cells in culture into cells capable of producing tumors when injected into animals.

This paper will review briefly the major types of relevant short‐term tests and will develop a rationale for a phased approach to the evaluation of the mutagenic and carcinogenic potential of environmental chemicals. This approach involves the sequential application of bioassays which are organized into a three‐level matrix emphasizing first detection, then confirmation, and finally hazard assessment. Chemicals demonstrating positive results in the short‐term detection systems and confirmatory bioassays are pursued in higher level whole animal tests. A core battery of tests is proposed to operationally define a negative result. The phased approach should facilitate a cost effective utilization of limited testing resources and provide protection for human health in proportion to the anticipated hazard.

Results obtained in evaluating a series of thirty‐eight pesticide chemicals according to the phased approach are discussed in detail.     

Hydroxypropyl-β-cyclodextrin as non-exhaustive extractant for organochlorine pesticides and polychlorinated biphenyls in muck soil

Hydroxypropyl-β-cyclodextrin (HPCD) was used as a non-exhaustive extractant for organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) in muck soil. An optimized extraction method was developed which involved using a HPCD to soil mass ratio of 5.8 with a single extraction period of 20 h. An aging experiment was performed by spiking a muck soil with ¹³C-labeled OCs and non-labeled PCBs. The soil was extracted with the optimized HPCD method and Soxhlet apparatus with dichloromethane over 550 d periodically. The HPCD extractability of the spiked OCs was greater than of the native OCs. A decreased in HPCD extractability was observed for the spiked OCs after 550 d of aging and their extractability approached those of the natives. The partition coefficient between HPCD and soil (log K_CD-Soil) was negatively correlated with the octanol-water partition coefficient (log K_OW) with r² = 0.67 and p < 0.05.     

Studies on the dissipation of 14C‐DDT from water and solid surfaces

Abstract

Dissipation of ¹⁴C‐p,p'‐DDT from water was studied for 180 days under outdoor conditions. DDT dissipated rapidly with overall half‐life of 53 days. The main degradation products were p,p'‐DDE and p,p'‐DDD. A portion of ¹⁴C‐residues was found in the sediment plus biomass (pellet) and on the inner surface of the glass container. This amounted to 7.2 and 6.7% of the initially added radioactivity, respectively. After 6 months, bound¹⁴C was more as compared to extractable ¹⁴C and p,p'‐DDD was the major metabolite of p,p'‐DDT in the extractable fraction. DDT dissipated from clay plates under indoor conditions with an overall half‐life of 160 days.     

Alginate beads containing water treatment residuals for arsenic removal from water—formation and adsorption studies

Water treatment residuals (WTRs) produced in large quantities during deironing and demanganization of infiltration water, due to high content of iron and manganese oxides, exhibit excellent sorptive properties toward arsenate and arsenite. Nonetheless, since they consist of microparticles, their practical use as an adsorbent is limited by difficulties with separation from treated solutions. The aim of this study was entrapment of chemically pretreated WTR into calcium alginate polymer and examination of sorptive properties of the obtained composite sorbent toward As(III) and As(V). Different products were formed varying in WTR content as well as in density of alginate matrix. In order to determine the key parameters of the adsorption process, both equilibrium and kinetic studies were conducted. The best properties were exhibited by a sorbent containing 5 % residuals, formed in alginate solution with a concentration of 1 %. In slightly acidic conditions (pH 4.5), its maximum sorption capacity was 3.4 and 2.9 mg g^?1 for As(III) and As(V), respectively. At neutral pH, the adsorption effectiveness decreased to 3.3 mg As g^?1 for arsenites and to 0.7 mg As g^?1 for arsenates. The presence of carboxylic groups in polymer chains impeded in neutral conditions the diffusion of anions into sorbent beads; therefore, the main rate-limiting step of the adsorption, mainly in the case of arsenates, was intraparticle diffusion. The optimal condition for simultaneous removal of arsenates and arsenites from water by means of the obtained composite sorbent is slightly acidic pH, ensuring similar adsorption effectiveness for both arsenic species.     

Evaluation of C18 solid‐phase extraction cartridges for the isolation of select pesticides and metabolites

Abstract

Nine different C₁₈ solid‐phase extraction (SPE) cartridges were evaluated for their efficiency at extracting nine pesticides and two s‐triazine metabolites from spiked deionized water samples. The SPE cartridges were found to contain nitrogen (N) and/or phosphorus (P) contaminants and varied in their extraction efficiency for certain pesticides and metabolites. Four of the nine SPE cartridges gave acceptable (70 to 120%) pesticide and metabolite recovery percentages, while five cartridges had marginal (50 to 70%) to poor (< 50%) recoveries. Statistical analyses showed that the poor to marginal recoveries found for three compounds could not be explained by considering several indigenous chemical and physical traits of the cartridge. It is suggested that proper SPE cartridge selection for pesticide recovery should be evaluated using several different cartridges.     

A device for sampling the mud‐water interface in eutrophic lakes and bogs for residue analysis

Abstract

A tubular device has been developed making it possible to obtain layered samples of loosely aggregated, flocculent material from bogs or eutrophic lakes. The samples are up to 50 cm long and 15 cm in diameter. The sampler is free from protuberances and intact, layered samples can be taken. The tubular part of the sampler is about 85 em long, the walls of the lower 25‐cm portion harbouring a pneumatic closing mechanism which is controlled from above the water surface. An extendible handle for manipulating the sampler and for guiding it into place, is fastened to the upper end of the sampling tube. The performance and the operation of the sampler in the field are described.     

N1‐aryl‐N2‐dichloroacetyl glycine and alanineamides as selective safeners for corn against chloroacetanilide herbicides

Abstract

Structurally new N¹aryl‐N²‐dichloroacetyl glycine and alaninamides were prepared. Greenhouse experiments were conducted to determine the effectiveness of the new compounds in protecting corn seedlings from chloroacetanilide (acetochlor, alachlor, dimethachlor, metazachlor, metolachlor) injury using dichlormid and BASF‐145138 as standard safeners. High rates of chloroacetanilides caused significant injury to sensitive corn hybrids. The most acive derivatives reduced injury to corn from dimethachlor and metolachlor and lesser extent from acetochlor and metazachlor. The most effective derivatives of the new compounds displayed better safening activity than the standards. Some of the new compounds were found to be selective safeners when formulated as a tank mixture with metolachlor in a 1:33–100 safener‐to‐herbicide ratio showing the same or better activity than the standard used.

Nomenclature: BASF‐145138, 1‐dichloroacetyl‐hexahydro‐3,3,8α‐trimethyl‐pyrrolo‐[1,2‐α]—pyrimidin‐6‐(2H)‐one; EPTC, S‐ethyl‐N,N‐dipropylcarbamothioate; dichlormid, 2,2‐dichloro‐N,N‐di‐2‐propenyl acetamide; corn, Zea Mays L. ‘Pannonia SC’.     

Application of polyaniline-based adsorbents for dye removal from water and wastewater—a review

Environmental Science and Pollution Research - Several industries release varying concentration of dye-laden effluent with substantial negative consequences for any receiving environmental...     

Poly (ε-caprolactone) as substrate for water denitrification

In this paper, poly (ε-caprolactone) (PCL) was used as carbon source and biofilm supporter in a fixed bed bioreactor to biologically remove nitrate from drinking water. The experimental results showed that denitrifying microorganisms could easily adapt to PCL as carbon source and attach to the surface of PCL granules. The fine biofilm could form on the surface of PCL granules within 15 days. Denitrification rate was influenced by temperature greatly and it decreased sharply at low temperature (below 20°C) and it was strongly linearly correlated with influent DO level. The denitrification rate at DO 8.5 mg/L was 47.4% of the value at DO 1.4 mg/L. Fixed-bed bioreactor packed with PCL granules could remove 50 mg/L influent nitrate completely, but the effluent DOC and suspended matter level were high. Accordingly, post-treatment unit are needed to ensure the good quality of effluent. Nitrite level did not accumulate in the whole experiment. Microbial growth was the main reason for reactor clog.     

Residues of five pesticides in field‐treated alfalfa seeds and alfalfa sprouts

Abstract

Residues of five different pesticides applied to alfalfa seed crops were determined in the harvested seeds and in sprouts grown from these seeds. Although seeds are usually used for future production of alfalfa plants, some of these seeds may be sprouted for human food consumption. The pesticides studied — aldicarb (Temik®), chlorothalonil (Bravo®), chlorpyrifos (Lorsban®), methamidophos (Monitor®) and propargite (Comite®) — were applied at a normal usage rate and at two to three times that rate. Residues on the seeds and sprouts, if any, were insignificant at rates of application.     

Henry’s law constant measurements for formaldehyde and benzaldehyde as a function of temperature and water composition

Henry’s law constants H of formaldehyde and benzaldehyde were determined using a dynamic system based on the water/air equilibrium at the interface within the length of a microporous tube. The measurements were conducted over the range 273–293 K in (i) deionized water, (ii) 35 g L^?1 solution of NaCl simulating seawater and (iii) two nitric acid solutions, i.e. 0.63 and 6.3 wt%.In pure water, the obtained data were used to derive the following Arrhenius expressions: ln H = (6423 ± 542)/T ? (13.4 ± 2.0) and ln H = (6258 ± 280)/T ? (17.5 ± 1.0) for formaldehyde and benzaldehyde, respectively. The H values, calculated at 293 K from Arrhenius expressions cited above were the following (in units of M atm^?1): H = 5020 ± 1170 (formaldehyde), H = 47 ± 5 (benzaldehyde). The temperature dependence of H permits then to derive the solvation enthalpies for both compounds: ΔH_solv = ?(53.4 ± 4.5) kJ mol^?1 and ΔH_solv = ?(52.0 ± 2.3) kJ mol^?1 for formaldehyde and benzaldehyde, respectively.In 35 g L^?1 salt solution, the H values were 27–66% and 12–21% lower than their respective determinations in deionized water, for formaldehyde and benzaldehyde respectively. The observed salt effect was used to estimate the following Setschenow coefficients at 293 K for 0.6 M NaCl: formaldehyde (0.21) and benzaldehyde (0.09).In 6.3 wt% nitric acid solution, H values of benzaldehyde were approximately 30% higher than those found in pure water although no significant influence was observed for formaldehyde.Finally, our experimental data were then used to estimate the fractions of formaldehyde and benzaldehyde in atmospheric aqueous phase and their derived atmospheric lifetimes.     

Accelerated degradation of carbofuran in standing water from carbofuran‐retreated Azolla plots

Abstract

Carbofuran (2, 3‐dihydro‐2, 2‐dimethyl‐7‐benzofuranyl N‐methylcarbamate) was mixed with standing water from six flooded Azolla (a fern harboring a nitrogen fixing alga, Anabaena azollae) plots that had been regularly treated with carbofuran before. The insecticide completely disappeared in 5 to 10 days when mixed with water from three of the six plots. The enrichment culture, prepared by further additions of carbofuran to the standing water from an Azolla plot, degraded bendiocarb (2, 2‐dimethyl‐l, 3‐benzidioxol‐4‐yl‐N‐methylcarbamate), carbofuran and carbosulfan [2,3‐dihydro‐2,2‐dimethyl‐7‐benzofuranyl (di‐n‐butyl‐aoinosulfenyl) methyl‐carbamate ] in that order. Enrichment culture, upon sterilization by autoclavlng, lost its ability to degrade carbofuran. Evidently, accelerated degradation of carbofuran in standing water from retreated Azolla plots was mediated by microorganisms.     

Application of ozone for the removal of bisphenol A from water and wastewater – A review

The extensive use of Bisphenol A (BPA) in the plastics industry has led to increasing reports of its presence in the aquatic environment, with concentrations of ng L^?1 to μg L^?1. Various advanced oxidation processes, including ozonation, have been shown to effectively degrade BPA. This paper reviews the current advancements in using ozone to remove BPA from water and wastewater.Most of the published work on the oxidation of BPA by ozone has focused on the efficiency of BPA removal in terms of the disappearance of BPA, and the effect of various operational parameters such as ozone feed rate, contact time and pH; some information is available on the estrogenic activity of the treated water. Due to increasing operational reliability and cost effectiveness, there is great potential for industrial scale application of ozone for the treatment of BPA. However, there is a significant lack of information on the formation of oxidation by-products and their toxicities, particularly in more complex matrices such as wastewater, and further investigation is needed for a better understanding of the environmental fate of BPA.     

Valorization of solid waste products from olive oil industry as potential adsorbents for water pollution control—a review

The global olive oil production for 2010 is estimated to be 2,881,500 metric tons. The European Union countries produce 78.5 % of the total olive oil, which stands for an average production of 2,136,000 tons. The worldwide consumption of olive oil increased of 78 % between 1990 and 2010. The increase in olive oil production implies a proportional increase in olive mill wastes. As a consequence of such increasing trend, olive mills are facing severe environmental problems due to lack of feasible and/or cost-effective solutions to olive-mill waste management. Therefore, immediate attention is required to find a proper way of management to deal with olive mill waste materials in order to minimize environmental pollution and associated health risks. One of the interesting uses of solid wastes generated from olive mills is to convert them as inexpensive adsorbents for water pollution control. In this review paper, an extensive list of adsorbents (prepared by utilizing different types of olive mill solid waste materials) from vast literature has been compiled, and their adsorption capacities for various aquatic pollutants removal are presented. Different physicochemical methods that have been used to convert olive mill solid wastes into efficient adsorbents have also been discussed. Characterization of olive-based adsorbents and adsorption mechanisms of various aquatic pollutants on these developed olive-based adsorbents have also been discussed in detail. Conclusions have been drawn from the literature reviewed, and suggestions for future research are proposed.     

Procedure for the determination of 2,4‐D and dicamba in inhalation,dermal, hand‐wash,and urine samples from spray applicators

Abstract

Analytical procedures for the simultaneous determination of residues of 2,4‐D and dicamba from polyurethane foam plug air samplers, ethylene glycol impregnated glass‐fiber filter paper dermal samplers, 1% sodium bicarbonate hand wash solution, and urine are presented. Residues were derivatized with diazomethane and quantitated using electron capture gas chromatography. Recoveries were greater than 80% at the limit of detection in all substrates. The limits of detection for both herbicides were 0.1 μg/foam plug and 0.5 μg/filter paper, and in the urine, 1.7 μg/100 mL and 5.0 μg/100 mL for dicamba and 2,4‐D, respectively.     

Persistence of residues in water and sediment op a fresh‐water lake after surface application of technical chlordane

Abstract

A fresh‐water lake, free from detectable pesticide residues before this study, was treated with a commercial formulation of technical chlordane. Water and sediment samples were analysed for chlordane residues 7, 24, 52, 279. and 421 days after treatment. Residues moved rapidly from the water to the lake bottom, supporting earlier results of a laboratory study with other organochlorines.

In water, α‐ and γ‐chlordane concentrations remained proportional to total chlordane concentrations, as determined by total‐peak area measurements of gas‐liquid chronatogrammes. But in bottom sediments, α‐ and γ‐chlordane were more persistent than other constituents of technical chlordane, supporting recent evidence that quantification of technical chlordane residues on the basis of γ‐chlordane quantification only (or that of a‐ and γ‐chlordane only), can lead to incorrect results and that this method, although simple and fast, should no longer be recommended.     

Applicability of MIEX®DOC process for organics removal from NOM laden water

The aim of this study was to evaluate applicability of ion exchange process for organics removal from Douro River surface water at the intake of Lever water treatment plant using magnetized ion exchange resin MIEX®. Qualitative analysis of the natural organic matter present in the surface water and prediction of its amenability to removal in conventional coagulation process were assessed. Results obtained in MIEX®DOC process kinetic batch experiments allowed determination of ion exchange efficiency in dissolved organic carbon (DOC), UV absorbing organics, and true color removal. The data were compared with the efficiencies of the conventional unit processes for organics removal at Lever WTP. MIEX®DOC process revealed to be more efficient in DOC removal than conventional treatment achieving the efficiencies in the range of 61–91 %, lowering disinfection by-products formation potential of the water. DOC removal efficiency at Lever WTP depends largely on the raw water quality and ranges from 28 % for water of moderated quality to 89 % of significantly deteriorated quality. In this work, MIEX®DOC process was also used as a reference method for the determination of contribution of anionic fraction to dissolved organic matter and selectivity of the unit processes at Lever WTP for its removal.     

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of São Paulo State,Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05–0.92, 0.12–11.01, 0.02–0.25 ng g⁻¹ dry wt, respectively, and in the surface water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l⁻¹, respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport.