Estimating Contributions of Nitrate and Herbicides From Groundwater to Headwater Streams,Northern Atlantic Coastal Plain,United States1

Abstract: Groundwater transport often complicates understanding of surface‐water contamination. We estimated the regional flux of nitrate and selected herbicides from groundwater to nontidal headwater streams of the Atlantic Coastal Plain (New Jersey through North Carolina) based on late‐winter or spring base‐flow samples from 174 streams. Sampled streams were selected randomly, and flux estimates are based on resulting population estimates rather than on empirical models, which have been used previously for similar estimates. Base‐flow flux in the estimated 8,834 headwater streams of the study area are an estimated 21,200 kg/day of nitrate (as N) and 5.83, 0.565, and 20.7 kg/day of alachlor, atrazine, and metolachlor (and selected degradates), respectively. Base‐flow flux of alachlor and metolachlor is <3% of the total base‐flow flux of those compounds plus degradates. Base‐flow flux of nitrate and herbicides as a percentage of applications is typically highest in well‐drained areas and lowest in areas with abundant poor drainage and anoxic conditions. In Coastal Plain watersheds of Albemarle and Pamlico Sounds, <2% of applied nitrogen reaches headwater streams as base flow. On the Delmarva Peninsula part of the Chesapeake Bay watershed, however, more than 10% of such applications are transported through groundwater to streams, and base‐flow nitrate flux represents 70% of total nitrogen flux in headwater streams.     

Potential Impacts of Stormwater Runoff on Water Quality in Urban Sand Pits and Adjacent Groundwater1

Whittemore, Donald O., 2012. Potential Impacts of Stormwater Runoff on Water Quality in Urban Sand Pits and Adjacent Groundwater. Journal of the American Water Resources Association (JAWRA) 48(3): 584-602. DOI: 10.1111/j.1752-1688.2011.00637.x Abstract: Entrance of stormwater runoff into water-filled pits and adjacent aquifers is a contamination concern. The water and sediment quality in several sand pits and surrounding groundwater in Wichita, Kansas, were studied to comprehensively address stormwater runoff impact. The pits are used for residential development after sand and gravel mining. Water samples were analyzed for inorganic constituents, bacteria, and 252 organic compounds, and pit sediments for inorganic components and 32 organic chemicals. Although many pesticide and degradate compounds were found in the pit and well waters, none of these chemicals exceeded existing health levels. Other organic contaminants were detected in the waters, with those exceeding health levels at one site attributed to an undiscovered groundwater contamination plume and not to stormwater runoff. Persistent insecticides and polychlorinated biphenyls detected in sediment of two pits are related to the age of residential development. The concentration distributions of pesticides and other organics at most of the sites, as well as iron, manganese, and ammonia patterns in downgradient well waters relative to upgradient well and pit waters, indicate that groundwater quality at the sites is affected by contaminants entering the pit surface waters. Thus, although current stormwater runoff does not appear to have contaminated sand-pit water and adjacent groundwater above health levels, the data show that the potential exists if stormwater became polluted.     

Heterogeneous reactions of suspended parathion, malathion, and fenthion particles with NO(3) radicals

Organophosphorus pesticides (OPPs) emit into the atmosphere in both gas and particulate phases via spray drift from treatments and post-application emission, but most of their degradations in the atmosphere are not well known. In this study, the heterogeneous reactions of nitrate (NO₃) radicals with three typical OPPs (parathion, malathion, and fenthion) absorbed on azelaic acid particles are investigated using an online vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The reaction products observed with the VUV-ATOFMS are identified on the basis of GC/MS analysis of the products in the reaction between NO₃ radicals and the coating of the pesticide. Paraoxon is identified as the only product of parathion; malaoxon and bis(1,2-bis-ethoxycarbonylethyl)disulfide as the products of malathion; fenoxon, fenoxon sulfoxide, fenthion sulfoxide, fenoxon sulfone, and fenthion sulfone as the products of fenthion. The degradation rates of parathion, malathion, and fenthion under the experimental conditions are 5.5 × 10⁻³, 5.6 × 10⁻², and 3.3 × 10⁻² s⁻¹, respectively. The pathways of the heterogeneous reactions between the three OPPs and NO₃ radicals are proposed. The experimental results reveal the possible transformations of these OPPs through the oxidation of NO₃ radicals in the atmosphere.     

Polychlorobiphenyls and organochlorine pesticides in conventional and organic brands of milk: occurrence and dietary intake in the population of the Canary Islands (Spain)

The population of the Spanish archipelago of the Canary Islands has been studied in depth regarding its levels of contamination by organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs). Foodstuffs of animal origin, such as milk, are prominent contributors to the body burden of these contaminants. As this population presents one of the highest milk-intake in Spain and Europe, we evaluated the level of OCs and PCBs in 26 commercially available brands of milk (16 conventional and 10 organic brands) present in the market of these Islands, in order to estimate the relevance of milk as a source of these chemicals for the Canary population. Our findings showed that hexachlorobenzene, trans-chlordane, and PCB153 were present in almost all the samples with independence of the type of milk. For both types of milks, the concentration of OCs was very low, showing organic milks lower levels than conventional ones. As a consequence, the estimated daily intake for OCs was lower than the tolerable daily intake (TDI) established by International Agencies. The levels of PCBs in milk were also found to be very low, but, in this case, the situation was the opposite: there were higher levels of PCBs in organic than in conventional brands of milk. Unexpectedly, levels of dioxin-like PCBs (DL-PCBs) reached values higher than 25 pg WHO-TEQ g⁻¹ fat in percentile 75 for both types of milk indicating the existence of a number of brands of milk highly contaminated by these toxicants. Consequently, the population who consume the most contaminated milk brands could have estimated daily intakes well above the recommended TDI (2 pg WHO-TEQ kg⁻¹ b.w. d⁻¹) established by European Union Authorities. These results are of concern if we consider the well known adverse health effects exerted by dioxin-like compounds.     

Partitioning of persistent organic pollutants (POPs) between human serum and breast milk: A literature review

The literature was reviewed to assess the relationship between the lipid adjusted concentration in human serum and breast milk (expressed as the serum/milk ratio) of a broad range of POPs in paired samples. Thirteen studies were identified, including seven studies that reported serum/milk ratios for polychlorinated dibenzo-dioxins and -furans (PCDD/Fs), ten for polychlorinated biphenyls (PCBs), five for polybrominated diphenyl ethers (PBDEs), and five for organochlorine pesticides (OCPs). Mean serum/milk ratios ranged between 0.7 and 25 depending on the compound and congener. For PCDD/Fs, PCBs and PBDEs, a clear trend of increasing mean serum/milk ratio by increasing molar volume, hydrophobicity and number of halogen substitutes was observed. The mean serum/milk ratios reported by the 13 studies summarized here will aid comparison between human POPs exposure studies using either serum or milk samples. More studies are needed to allow a valid comparison between data obtained from analysis of breast milk and serum samples for a broader range of POPs. Furthermore such studies may shed light on compound specific factors as well as other determinants that may affect the partitioning and partition kinetics of POPs between serum and breast milk.     

Assessment of GC–MS response of selected pesticides in apple matrices related to matrix concentration

A uniform analyte response is required for GC–MS analysis in order to obtain acceptable quantitative results. The response of pesticides in complex matrices is susceptible to variation due to the interactions of co-extractives, both with pesticides or with GC–MS system. This study was conducted to determine the magnitude of the interactions, called matrix effect, and their behavior with the matrix dilution. The response of pyrimethanil (4,6-dimethyl-N-phenylpyrimidin-2-amine), cyprodinil (4-cyclopropyl-6-methyl-N-phenylpyrimidin-2-amine), trifloxystrobin (methyl-(2Z)-2-methoxyimino-2-[2-[[(E)-1-[3(trifluoromethyl)phenyl]ethylidene amino]oxymethyl]phenyl]acetate) and bifenthrin(2-methyl-3-phenylphenyl)methyl-3-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate), used in apple crops protection, was evaluated in different concentrations of peel and flesh extracts of Granny Smith, Golden Delicious and Demi Rouge, selected as representatives of different matrix types. The matrix effect ranged from ?0.05 to 146.14%, depending on matrix type and pesticide. The highest response variation was observed in extracts of Granny Smith—an enhancement in flesh and suppression in peel extract. With the dilution, the matrix effect decreased with different magnitudes, but for Granny Smith peel extract an inverted effect was observed. The presence of the matrix effect in GC–MS pesticides analysis was obvious, requiring the application of matrix-matched calibration in quantification procedures for each variety, with calibration standards matched by the matrix concentration.     

N-methylcarbamate pesticides and their phenolic degradation products: hydrolytic decay,sequestration and metal complexation studies

We report on the rates of decomposition of a group of N-methylcarbamate (NMC) pesticides (carbaryl, carbofuran and propoxur) under pre-determined tropical field conditions. Rates of decomposition for three NMCs were determined at pH 7.08 and T?=?20?°C and pH 7.70 and T = 33?°C respectively, as follows: carbaryl (78?days and 69?days); carbofuran (143?days and 83?days) and propoxur (116?days and 79?days). Investigation on methods for removal of NMCs and their phenolic decomposition products shows that activated charcoal outperforms zeolite, alumina, diatomaceous earth, cellulose and montmorillonite clay in the removal of both NMCs and phenols from aqueous solution. Furthermore, metal complexation studies on the NMCs and phenols showed that Fe (III) forms a complex with isopropoxyphenol (IPP) within which the Fe:IPP ratio is 1:3, indicative of the formation of a metal chelate complex with the formula Fe(IPP)₃.     

Utilization of long duration high-volume sampling coupled to SPME-GC-MS/MS for the assessment of airborne pesticides variability in an urban area (Strasbourg,France) during agricultural application

Atmospheric samples have been collected between 14 March and 12 September 2012 on a 2-week basis (15 days of sampling and exchange of traps each 7 days) in Strasbourg (east of France) for the analysis of 43 pesticides. Samples (particle and gas phases) were separately extracted using Accelerated Solvent Extraction (ASE) and pre-concentrated by Solid Phase Micro-Extraction (SPME) before analysis by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Four SPME consecutive injections at distinct temperatures were made in order to increase the sensitivity of detection for the all monitored pesticides. Currently used detected pesticides can be grouped in four classes; those used in maize crops (acetochlor, benoxacor, dicamba, s-metolachlor, pendimethalin, and bromoxynil), in cereal crops (benoxacor, chlorothalonil, fenpropimorph, and propiconazole), in vineyards (tebuconazole), and as herbicides for orchards, meadows of green spaces (2,4-MCPA, trichlopyr). This is in accordance with the diversity of crops found in the Alsace region and trends observed are in accordance with the period of application of these pesticides. Variations observed permit also to demonstrate that the long time sampling duration used in this study is efficient to visualize temporal variations of airborne pesticides concentrations. Then, long time high-volume sampling could be a simple method permitting atmospheric survey of atmospheric contamination without any long analysis time and consequently low cost.     

舟山近岸海域贝类中有机氯农药残留水平及人体健康风险评估

于2012年的7月在舟山群岛新区的海域采集贝类样本,测定了其中的有机氯农药残留量,并进行了人体健康风险评估和安全食用量推算。结果表明,采集的5种贝类样本中,六六六(BHCs)的各组分均未被检出,而滴滴涕(DDTs)在各种样本中均有检出,其中僧帽牡蛎和部分縊蛏样本中DDTs总量超过《海洋生物质量标准》(GB 18421—2001)一类标准(10μg/kg);健康风险评估结果显示,贝类样本中α-BHC、β-BHC、γ-BHC、p,p’-滴滴伊(p,p’-DDE)、p,p’-滴滴滴(p,p’-DDD)、p,p’-DDT的总致癌风险指数均低于10-4,致癌风险均在可接受的安全范围,α-BHC、β-BHC、γ-BHC、p,p’-DDE的总接触风险指数均小于1,接触风险指数未超过危害剂量参考值,人体食用舟山近岸海域的贝类是安全的;按可接受的致癌风险指数进行评估,人体的贝类安全消费量为9.8~138.0g/(kg·d)(按体重计,下同),而按可接受的接触风险指数进行评估,人体的贝类安全消费量在24.6~235.0g/(kg·d)。     

A novel pretreatment approach for fast determination of organochlorine pesticides in biotic samples

Recent studies have focused on enantiomeric behaviors of chiral organochlorine pesticides (OCPs) in biotic matrix because they provide insights into the biotransformation processes of chiral OCPs. In the present paper, a double in-line column chromatographic method was developed to effectively remove the lipid impurity in different biotic samples for clean-up of OCPs. After an initial Soxhlet extraction of OCPs from the biotic samples by a mixture of acetone and dichloromethane (DCM), dimethyl sulfoxide (DMSO) was directly added to the extract, and low boiling point solvents (acetone and DCM) were then evaporated. OCPs remained in DMSO were eluted via column 1 filled with silicon gel, and subsequently passed through column 2 packed with 15% deactivated florisil. This novel method was characterized by significant time and solvent savings. The recovery rates of α -HCH (hexachlorocyclohexane), β -HCH, γ -HCH and δ -HCH were 78.5 ± 3.1%, 72.4 ± 7.7%, 72 ± 4.0% and 70.0 ± 8.7%, respectively, and 92.5 ± 3.8%, 79.7 ± 6.7% and 83.4 ± 6.5% for 1,1-dichloro-2-(2-chlorophenyl)-2-(4- chlorophenyl) ethylene (o,p′-DDE), 1,1-dichloro-2-(2-chlorophenyl)-2-(4-chloro phenyl)ethane (o,p′-DDD) and 1,1,1-trichloro-2-(2-chlorophenyl)-2-(4-chlorophenyl) ethane (o,p′-DDT), separately. In addition, the separation efficiencies of the target compounds by both achiral and chiral gas chromatographic columns were satisfactory using the established method. Therefore, the double in-line column chromatography was a useful alternative method for pretreatment of OCPs in different biotic samples.