Bioaccessibility of environmentally aged 14C-atrazine residues in an agriculturally used soil and its particle-size aggregates

After 22 years of aging under natural conditions in an outdoor lysimeter the bioaccessibility of 14C-labeled atrazine soil residues to bacteria was tested. Entire soil samples as well as sand-sized, silt-sized, and clay-sized aggregates (>20, 20-2, and <2microm aggregate size, respectively) were investigated under slurried conditions. The mineralization of residual radioactivity in the outdoor lysimeter soil reached up to 4.5% of the total 14C-activity after 16 days, inoculated with Pseudomonas sp. strain ADP. The control samples without inoculated bacteria showed a mineralization maximum of only about 1% after 44 days of incubation. Mineralization increased in the clay-sized aggregates up to 6.2% of the total residual 14C-activity within 23 days. With decreasing soil aggregate sizes, residual 14C-activity increased per unit of weight, but only minor differences of the mineralization in the soil and soil size aggregates using mineral-media for incubation was observed. Using additional Na-citrate in the incubation, the extent of mineralization increased to 6.7% in soil after 23 days following incubation with Pseudomonas sp. strain ADP. These results show that long-term aged 14C-atrazine residues are still partly accessible to the atrazine degrading microorganism Pseudomonas sp. strain ADP.     

Atrazine,deethylatrazine, and deisopropylatrazine in surface runoff from conservation tilled watersheds

Atrazine and two of its metabolites, deethylatrazine (DEA) and deisopropylatrazine (DIA), are frequently detected in surface runoff. Although their health and environmental effects may be similar to that of atrazine and ratios of their concentrations are useful in delineating sources of contamination, there have been few long-term studies of the factors affecting their losses in runoff. Therefore, losses of atrazine, DEA, and DIA were monitored for six years in runoff from seven small (0.45-0.79 ha) watersheds under three tillage practices. Weather year and the timing of runoff-producing rainfall had a greater effect on atrazine, DEA, and DIA concentrations and losses than did tillage practice. DEA was the most frequently detected metabolite with an average concentration in the year of atrazine application, of 2.5 microg L(-1) compared to 0.7 microg L(-1) for DIA. Atrazine exceeded its 3 /g L(-1) maximum contaminant level (MCL) up to 100 days after application. DEA and DIA exceeded the atrazine MCL up to 50 days after atrazine application; thus, failure to monitor their presence may result in underestimation of the environmental impact of atrazine usage. The molar concentration ratio of DEA to atrazine (DAR) was affected by tillage treatment, weather year, and possibly soil type. These factors may need to be taken into account when DAR is used as an index of atrazine movement. The ratio of DIA to DEA (D2R) was fairly constant and should be useful in determining the parent compounds contributing DIA to surface waters.     

Field demonstration of successful bioaugmentation to achieve dechlorination of tetrachloroethene to ethene

A laboratory microcosm study and a pilot scale field test were conducted to evaluate biostimulation and bioaugmentation to dechlorinate tetrachloroethene (PCE) to ethene at Kelly Air Force Base. The site groundwater contained about 1 mg/L of PCE and lower amounts of trichloroethene (TCE) and cis-1,2-dichloroethene (cDCE). Laboratory microcosms inoculated with soil and groundwater from the site exhibited partial dechlorination of TCE to cDCE when amended with lactate or methanol. Following the addition of a dechlorinating enrichment culture, KB-1, the chlorinated ethenes in the microcosms were completely converted to ethene. The KB-1 culture is a natural dechlorinating microbial consortium that contains phylogenetic relatives of Dehalococcoides ethenogenes. The ability of KB-1 to stimulate biodegradation of chlorinated ethenes in situ was explored using a closed loop recirculation cell with a pore volume of approximately 64,000 L The pilot test area (PTA) groundwater was first amended with methanol and acetate to establish reducing conditions. Under these conditions, dechlorination of PCE to cDCE was observed. Thirteen liters of the KB-1 culture were then injected into the subsurface. Within 200 days, the concentrations of PCE, TCE, and cis-1,2-DCE within the PTA were all below 5 microg/L, and ethene production accounted for the observed mass loss. The maximum rates of dechlorination estimated from field date were rapid (half-lives of a few hours). Throughout the pilot test period, groundwater samples were assayed for the presence of Dehalococcoides using both a Dehalococcoides-specific PCR assay and 16S rDNA sequence information. The sequences detected in the PTA after bioaugmentation were specific to the Dehalococcoides species in the KB-1 culture. These sequences were observed to progressively increase in abundance and spread downgradient within the PTA. These results confirm that organisms in the KB-1 culture populated the PTA aquifer and contributed to the stimulation of dechlorination beyond cDCE to ethene.     

Impacts of aging on in vivo and in vitro measurements of soil-bound polycyclic aromatic hydrocarbon availability

Ingestion of contaminated soil is an exposure pathway at approximately one-half of the Superfund sites in the United States. This study was designed to evaluate the impacts of aging in soil on the availability of polycyclic aromatic hydrocarbons (PAHs). Two coal tar (CT)-amended soils were prepared. One was aged for 270 days and the other was not aged. Both of these treatments were incorporated into pellets and fed to male Fischer 344 rats. Excretion of 1-hydroxypyrene (1-OHP) in urine and PAH concentrations in the liver were monitored as end points. Additionally, soil:water partitioning and desorption were measured as comparisons to the in vivo results. After 5 days of ingesting their respective treatments, rats in the aged soil group excreted 4.41 +/- 1.67 ppm 1-OHP/mg of pyrene ingested while rats in the unaged soil group excreted 5.27 +/- 1.37 ppm/mg of pyrene ingested. Animals fed aged CT soil had 0.051 +/- 0.011 ppm carcinogenic PAHs in livers/mg ingested while rats fed unaged CT soil had 0.063 +/- 0.037 ppm carcinogenic PAHs in livers/mg ingested. Partitioning and desorption results revealed a similar results. These results indicate that, at high application rates, soil contact time may not play as significant a role in determining availability as simple dispersion and sorption on soil.     

Variation in arsenic speciation and concentration in paddy rice related to dietary exposure

Ingestion of drinking water is not the only elevated source of arsenic to the diet in the Bengal Delta. Even at background levels, the arsenic in rice contributes considerably to arsenic ingestion in subsistence rice diets. We set out to survey As speciation in different rice varieties from different parts of the globe to understand the contribution of rice to arsenic exposure. Pot experiments were utilized to ascertain whether growing rice on As contaminated soil affected speciation and whether genetic variation accounted for uptake and speciation. USA long grain rice had the highest mean arsenic level in the grain at 0.26 microg As g(-1) (n = 7), and the highest grain arsenic value of the survey at 0.40 microg As g(-1). The mean arsenic level of Bangladeshi rice was 0.13 microg As g(-1) (n = 15). The main As species detected in the rice extract were AsIII, DMAV, and AsV. In European, Bangladeshi, and Indian rice 64 +/- 1% (n = 7), 80 +/- 3% (n = 11), and 81 +/- 4% (n = 15), respectively, of the recovered arsenic was found to be inorganic. In contrast, DMAV was the predominant species in rice from the USA, with only 42 +/- 5% (n = 12) of the arsenic being inorganic. Pot experiments show that the proportions of DMAV in the grain are significantly dependent on rice cultivar (p = 0.026) and that plant nutrient status is effected by arsenic exposure.     

A model for the effect of rhizodeposition on the fate of phenanthrene in aged contaminated soil

Microcosm data were used to develop a deterministic model to describe how rhizodeposition affects the fate of phenanthrene in aged contaminated soil. Microbial mineralization and soil sequestration of 14C-phenanthrene were compared in microcosms amended weekly with phenolic-rich mulberry root extracts versus unamended controls. Mineralization was higher in the amended soils simulating the rhizosphere (57.7 +/- 0.9%) than in controls simulating bulk (unplanted) soils (53.2 +/- 0.7%) after 201 days (p < 0.05). Humin was the main soil sink for the residual 14C-label. Whereas the total 14C-label associated with humin remained constant in biologically active soils (at about 30%), it increased up to 80% after 201 days in sterile controls. The initial phenanthrene extraction with n-butanol (commonly used to assess bioavailability) slightly underestimated the fraction thatwas mineralized (assessed by 14CO2 recovery). Changes in the unextractable fraction (determined by combustion in a biological oxidizer) suggested the presence of two soil sequestration domains: (1) irreversibly bound residue, and (2) an intermediate transition phase that is unextractable by solvents at a given point in time but could become bioavailable due to physicochemical or biological transformations of the binding matrix. The fate of phenanthrene was accurately modeled by considering the transfer of the 14C label between different soil compartments as first-order kinetic processes. Model simulations suggested that the system was approaching a stable end-point after 201 days of simulated rhizoremediation, and corroborated that microorganisms have a significant impact on the fate of phenanthrene in soil.     

Biofiltration of residual fertilizer nitrate and atrazine by Rhizobium meliloti in saturated and unsaturated sterile soil columns

This study was undertaken to investigate whether microbial bioaugmentation of subsurface soil with subsurface irrigation could be used as a biofiltration/biocontrol technology for agricultural pollutants. Nine Plexiglas columns, 458 mm long x 139 mm in diameter, were packed with a sterilized sandy loam soil. Subsurface irrigation, through a controlled water table management system, was used to deliver bacteria, Rhizobium meliloti A-025, to the soil and to maintain aerobic (unsaturated) or anaerobic (saturated) conditions in the columns. Nitrate and atrazine, a fertilizer and a corn herbicide, were applied to the soil surface, and leaching was affected by simulated rainfall events. The soil and drainage waters were analyzed for nitrate and atrazine residues after each rainfall simulation throughout the experimental period during which the soil was kept saturated for a total of 80 days and unsaturated for a total of 70 days. The monitoring of transport and survival of the implanted bacterial strain (A-025) showed that subsurface irrigation was successful in introducing and transporting the bacteria throughout the soil columns. During the saturated period, significantly more (95% probability) nitrate-N leached into the drainage waters from the control columns than from the bioaugmented columns; the increase being 450% or more for the abiotic control columns. The amount of atrazine that leached into the drainage waters during the unsaturated period was also significantly more from control columns as opposed to bioaugmented columns, with the increase being 262%.     

Percutaneous absorption of 4-cyanophenol from freshly contaminated soil in vitro: effects of soil loading and contamination concentration

Despite the skin's excellent barrier function, dermal exposure to soil contaminated with toxic chemicals can represent a significant health hazard (e.g., via multiple work related contacts in the farming and waste disposal industries). The development of environmental standards or limits for chemical levels in soil has been impeded because quantification of percutaneous uptake from this medium has not been well-defined. The objective of the research described here, therefore, was to better characterize the rate and extent of dermal penetration as a function of soil loading and degree of soil contamination. The absorption of a model compound (4-cyanophenol, CP) across hairless mouse skin in vitro has been determined at four different soil loadings (5, 11, 38 and 148 mg cm-2) and at six levels of soil contamination (concentrations ranging from 0.19 to 38 mg/g soil). Following 8 h of exposure, the amount of CP absorbed was independent of soil loading when CP concentration was constant, implying that the quantity of soil presentwas always sufficientto provide atleast a single layer of tightly packed particles. At the lowest loadings, however, with increasing times of exposure, the CP transport rate fell off due to depletion of chemical from the soil. At constant soil loading (38 mg cm(-2)), CP flux (Jss) across the skin was linearly proportional to the level of contamination (C(o)soil) over the range 0.19 to 23.5 mg of CP per gram of soil: Jss (micorg cm(-2) h(-1)) = (1.1 x 10(-5) g cm(-2) h(-1)) x Csoil (microg/g soil). At the highest CP contamination concentration, however, the transport rate was about an order of magnitude higher than expected, possibly due to the presence of pure CP crystals. In conclusion, these results provide new quantifications of the characteristics of dermal uptake from chemically contaminated soils and important information with which to develop and verify predictive models of dermal absorption.     

Bioremediation of diethylhexyl phthalate contaminated soil: a feasibility study in slurry- and solid-phase reactors

The aim of the research was to verify the possibility of applying bioremediation as a treatment strategy on a poly(vinyl chloride) (PVC) manufacturing site in the north of Italy contaminated by diethylhexyl phthalate (DEHP) at a concentration of 5.51 mg/g of dry soil. Biodegradation kinetic experiments with DEHP contaminated soil samples were performed in both slurry- and solid-phase systems. The slurry-phase results showed that the cultural conditions, such as N and P concentrations and the addition of a selected DEHP degrading strain, increased the natural DEHP degradation rate. On the basis of these data, experiments to simulate bioventing on contaminated soil columns were performed. The DEHP concentration reached 0.63 mg/g of dry soil in 76 days (89% of degradation). A kinetic equation was developed to fit the experimental data and to predict the concentration of contaminant after treatment. The data obtained are encouraging for a future in situ application of the bioventing technology.     

Total and inorganic arsenic concentrations in rice sold in Spain, effect of cooking, and risk assessments

Rice can contain a relatively high amount of arsenic (As). We evaluated total and inorganic As concentrations in 39 samples of different types of rice sold in Spain. The analyses were performed in raw rice and in rice cooked by boiling to dryness in water spiked with As(V) (0.1-1 microg mL(-1)). In raw rice, inorganic As represented 27-93% of total As: total As = 0.188 +/- 0.078 microg g(-1) dry weight (dw); inorganic As = 0.114 +/- 0.046 microg g(-1) dw. After cooking, the rice retained between 45% and 107% of the As(V) added to the cooking water, and the inorganic As concentrations ranged between 0.428 microg g(-1) dw (0.1 microg mL(-1) in the cooking water) and 3.89 microg g(-1) dw (1.0 microg microL(-1) in the cooking water). For raw rice, the inorganic As intake of the Spanish population (16 g raw rice/day) remains below the tolerable daily intake (TDI) proposed by the WHO (2.1 microg inorganic As/day/kg body weight). In rice cooked with water contaminated with As(V), this cereal intake is sufficient to attain the TDI. The results reveal the need to consider the determination of inorganic As and the influence of cooking when evaluating the risks associated with the consumption of rice.     

Spatial distribution and temporal variability of arsenic in irrigated rice fields in Bangladesh. 1. Irrigation water

Around 38% of the area of Bangladesh is irrigated with groundwater to grow dry season crops, most importantly boro rice. Due to high As concentrations in many groundwaters, over 1000 tons of As are thus transferred to arable soils each year, creating a potential risk for future food production. We studied the reactions and changing speciation of As, Fe, P, and other elements in initially anoxic water during and after irrigation and the resulting spatial distribution of As input to paddy soils near Sreenagar (Munshiganj), 30 km south of Dhaka, in January and April 2005 and February 2006. The irrigation water had a constant concentration of 397 +/- 7 microg L(-1) As (approximately 84% As(III)), 11 +/- 0.1 mg L(-1) Fe, and 2 +/- 0.1 mg L(-1) P. During the fast flow along the longest irrigation channel (152 m) As, Fe, and P speciation changed, but total concentrations did not decrease significantly, indicating that As input to fields was independent of the length of the irrigation channels. In contrast, during slow water flow across the fields, As, Fe, and P concentrations decreased strongly with increasing distance from the water inlet, due to formation and settling of As- and P-bearing Fe aggregates and by adsorption to soil minerals. Total As concentrations in field water were approximately 3 times higher close to the inlet than in the opposite field corner shortly after irrigation, and decreased to below 35 microg L(-1) over the next 72 h. The laterally heterogeneous transfer of As, Fe, and P from irrigation waterto soil has important consequences for their distribution in irrigated fields and needs to be considered in sampling and in assessing the dynamics and mass balances of As fluxes among irrigation water, soil, and floodwater.     

Arsenic contamination of Bangladesh paddy field soils: implications for rice contribution to arsenic consumption

Arsenic contaminated groundwater is used extensively in Bangladesh to irrigate the staple food of the region, paddy rice (Oryza sativa L.). To determine if this irrigation has led to a buildup of arsenic levels in paddy fields, and the consequences for arsenic exposure through rice ingestion, a survey of arsenic levels in paddy soils and rice grain was undertaken. Survey of paddy soils throughout Bangladesh showed that arsenic levels were elevated in zones where arsenic in groundwater used for irrigation was high, and where these tube-wells have been in operation for the longest period of time. Regression of soil arsenic levels with tube-well age was significant. Arsenic levels reached 46 microg g(-1) dry weight in the most affected zone, compared to levels below l0 microg g(-1) in areas with low levels of arsenic in the groundwater. Arsenic levels in rice grain from an area of Bangladesh with low levels of arsenic in groundwaters and in paddy soils showed that levels were typical of other regions of the world. Modeling determined, even these typical grain arsenic levels contributed considerably to arsenic ingestion when drinking water contained the elevated quantity of 0.1 mg L(-1). Arsenic levels in rice can be further elevated in rice growing on arsenic contaminated soils, potentially greatly increasing arsenic exposure of the Bangladesh population. Rice grain grown in the regions where arsenic is building up in the soil had high arsenic concentrations, with three rice grain samples having levels above 1.7 microg g(-1).     

Predicting atrazine levels in water utility intake water for MCL compliance

To protect human health, atrazine concentrations in finished municipal drinking water must not exceed a maximum contaminant level (MCL) of 3 microg/L, as determined by a specific monitoring regime mandated by the United States Environmental Protection Agency. Atrazine levels were monitored along tile-fed drainage ditches draining to a major drinking water source and used to predict MCL exceedance frequencies of intake and finished drinking water. Water samples were collected daily at eight monitoring sites located at the outlets of subbasins draining 298-19 341 ha (736-47 794 ac). Flow-weighted average (FWA) atrazine concentrations ranged from 0.9 to 9.8 microg/L, and were above 3 microg/L for the majority of sites, including the largest site, which represents water quality at the intake of the local municipal water treatment plant. However, a relatively low percentage of samples near the water utility intake exceeding 3 microg/L atrazine (10.4%) made this problem difficult to detect. In order to have a 95% probability of detecting any intake sample exceeding 3 microg/L atrazine in a drainage system exceeding 3 microg/L atrazine on a FWA basis, sampling frequency would need to be every 7 days or more often during the second quarter when the potentials for field atrazine losses and temporal variability of atrazine concentrations are highest.     

Comparative effects of dietary methylmercury on gene expression in liver, skeletal muscle, and brain of the zebrafish (Danio rerio)

Effects of dietary methylmercury (MeHg) on gene expression were examined in three organs (liver, skeletal muscle, and brain) of the zebrafish (Danio rerio). Adult male fish were fed over 7, 21, and 63 days on three different diets: one control diet (C0: 0.08 microg of Hg g(-1), dry wt) and two diets (C1 and C2) contaminated by MeHg at 5 and 13.5 microg of Hg g(-1), dry wt. Total Hg and MeHg concentrations were determined in the three organs after each exposure duration, and a demethylation process was evidenced only in the liver. Thirteen genes known to be involved in antioxidant defenses, metal chelation, active efflux of organic compounds, mitochondrial metabolism, DNA repair, and apoptosis were investigated by quantitative real-time RT-PCR and normalized according to actin gene expression. Surprisingly, no change in the expression levels of these genes was observed in contaminated brain samples, although this organ accumulated the highest mercury concentration (63.5 +/- 4.4 microg g(-1), dry wt after 63 days). This lack of genetic response could explain the high neurotoxicity of MeHg. coxI and cytoplasmic and mitochondrial sod gene expressions were induced early in skeletal muscle and later in liver, indicating an impact on the mitochondrial metabolism and production of reactive oxygen species. Results demonstrated that skeletal muscle was not only an important storage reservoir but was also affected by MeHg contamination. The expression of the metallothionein mt2 and the DNA repair rad51 genes was up-regulated in liver between 21 and 63 days, whereas in skeletal muscle, mt2 remained uninduced, and gadd and rad51 were found to be repressed.     

In vitro gastrointestinal bioavailability of arsenic in soils collected near CCA-treated utility poles

Because of the potentially high arsenic concentrations found in soils immediately adjacent to chromated copper arsenate (CCA)-treated wood structures and utility poles, CCA-contaminated soil ingestion may be a significant exposure route to arsenic for children. Therefore, a strong need exists to provide accurate data on oral relative bioavailability (RBA) of arsenic (in vivo or in vitro) in field-collected CCA-contaminated soils. The objectives of this study were (1) to assess arsenic bioaccessibility in contaminated soils collected near in-service CCA-treated utility poles, (2) to determine the influence of soil properties and arsenic fractionation on arsenic bioaccessibility, and (3) to estimate an average daily arsenic intake from incidental soil ingestion. Arsenic bioaccessibility (in vitro gastrointestinal (IVG) method) was determined on surface soil samples collected immediately adjacent to 12 CCA-treated utility poles after 18 months of service. Bioaccessible arsenic was also determined in 3 certified reference materials. Total arsenic concentrations in soils (<300 microm) varied from 37 +/- 2 to 251 +/- 12 mg/kg, irrespective of soil organic matter contentwith the major soil-bound arsenic species being As(V). Arsenic bioaccessibility ranged between 25.0 +/- 2.7 and 66.3 +/- 2.3% (mean value 40.7 +/- 14.9%). The mean value was in agreement with the in vivo arsenic RBA reported by Casteel et al. (2003) in soil near CCA-treated utility poles. Bioaccessible arsenic was positively correlated with total organic carbon content (r2 = 0.36, p < 0.05) and with water-soluble arsenic (2 = 0.51, p < 0.01), and was negatively correlated with clay content (r2 = 0.43, p < 0.05). Using conservative exposure parameters, the mean daily arsenic intake from incidental ingestion of contaminated soil near CCA-treated utility poles was 0.18 +/- 0.09 microg As kg(-1) d(-1). This arsenic intake appeared negligible compared to the daily intake of inorganic arsenic from water and food ingestion for children.     

Biodegradation of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) by Phanerochaete chrysosporium: new insight into the degradation pathway

Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) is a recalcitrant energetic chemical that tends to accumulate in soil, close to the surface. The present study describes the aerobic biodegradability of HMX using Phanerochaete chrysosporium. When added to 7 day old static P. chrysosporium liquid cultures, HMX (600 nmol) degraded within 25 days of incubation. The removal of HMX was concomitant with the formation of transient amounts of its mono-nitroso derivative (1-NO-HMX). The latter apparently degraded via two potential routes: the first involved N-denitration followed by hydrolytic ring cleavage, and the second involved alpha-hydroxylation prior to ring cleavage. The degradation of 1-NO-HMX gave the ring-cleavage product 4-nitro-2,4-diazabutanal (NDAB), nitrite (NO2 -), nitrous oxide (N2O), and formaldehyde (HCHO). Using [14C]-HMX, we obtained 14CO2 (70% in 50 days), representing three C atoms of HMX. Incubation of real soils, contaminated with either HMX (403 micromol kg(-1)) (military base soil) or HMX (3057 micromol kg(-1)), and RDX (342 micromol kg(-1)) (ammunition soil) with the fungus led to 75 and 19.8% mineralization of HMX (liberated 14CO2), respectively, also via the intermediary formation of 1-NO-HMX. Mineralization in the latter soil increased to 35% after the addition of glucose, indicating that a fungus-based remediation process for heavily contaminated soils is promising. The present findings improve our understanding about the degradation pathway of HMX and demonstrate the utility of using the robust and versatile fungus P. chrysosporium to develop effective remediation processes for the removal of HMX.     

Enhancing phenanthrene biomineralization in a polluted soil using gaseous toluene as a cosubstrate

Laboratory experiments were conducted to study the potential of adding gaseous toluene, as a readily degradable carbon source, to enhance phenanthrene mineralization in polluted soil (1,000 mg/kg(dry soil)) aged for 400 days. Experiments were conducted in 0.5-L column reactors packed with a mixture of (80:20 w(wet)/w(wet)) spiked soil and vermiculite and fed with 1 g m(-3)reactor h(-1) toluene load in air. Removal efficiencies of 100% for toluene and greater than 95% for phenanthrene were obtained in 190 h. Evolved CO2 showed that phenanthrene mineralization increased from 39% to 86% in columns treated with gaseous toluene. Phthalic acid was identified as the principal soluble intermediate, which accumulated when no toluene was added. Increased phenanthrene uptake and mineralization with toluene can be attributed to increased biomass and the induction of enzymes involved in the intermediate mineralization. In microcosm experiments, phthalic acid mineralization increased from 19% to 81% within 50 h in the presence of toluene. Experiments with 14C-labeled phenanthrene confirmed the enhancement of phenanthrene mineralization from 45% to 83% in 385 h with toluene as a second carbon source. The results indicate thatthe addition of an appropriate gaseous cosubstrate could be an adequate strategy to enhance mineralization of PAHs in soil.     

Solid-phase microextraction-liquid chromatography-mass spectrometry applied to the analysis of insecticides in honey.

An approach based on solid-phase microextraction-liquid chromatography-mass spectrometry (SPME-LC-MS) has been developed for determining 12 insecticides (bromophos ethyl, chlorpyrifos methyl, chlorpyrifos ethyl, diazinon, fenoxycarb, fonofos, phenthoate, phosalone, pirimiphos methyl, profenofos, pyrazophos, and temephos) in honey. The influence of several parameters on the efficiency of the SPME was systematically investigated. Under optimal conditions, the procedure provided excellent linearity (>0.990), detection and quantification limits (between 0.001 and 0.1 microg g(-1) and between 0.005 and 0.5 microg g(-1), respectively), and precision (<19% at the quantification limits and from 6 to 14% at ten times higher concentrations). However, recoveries were not so good, ranging from 19 to 92%. Honey samples were found that were contaminated with bromophos ethyl, diazinon, fonofos, pirimiphos ethyl, pyrazophos, and temephos at estimated concentrations from 6.2 +/- 1.2 to 19 +/- 3 ng g(-1).     

Oxidation products of polyunsaturated fatty acids in infant formulas compared to human milk--a preliminary study

Information about lipid oxidation in fresh and stored human milk compared with infant formulas is scarce. We aimed to assess n-6 and n-3 PUFA oxidation in these milks by measuring the 4-hydroxynonenal (4-HNE) and 4-hydroxyhexenal (4-HHE) content. Human milk samples (n = 4), obtained from volunteer mothers, were analyzed fresh and after 1 wk at 4 degrees C or 24 h at 18 degrees C. Vitamin E and malondialdehyde (MDA) were measured by HPLC and fatty acid profile by GC. The 4-HHE and 4-HNE contents were measured by GC-MS. Infant formulas (n = 10) were tested; their fat droplet size was measured by laser light scattering and observed by confocal laser scanning microscopy. Human milk samples contained 31.0 +/- 6.3 g/L of lipids and 1.14 +/- 0.26 mg/L of vitamin E. Fat droplets were smaller in infant formulas than reported in human milk. The (4-HHE/n-3 PUFA) ratio was 0.19 +/- 0.01 microg/g in fresh human milk (unchanged after storage) versus 3.6 +/- 3.1 microg/g in dissolved powder formulas and 4.3 +/- 3.8 microg/g in liquid formula. (4-HNE/n-6 PUFA) was 0.004 +/- 0.000 microg/g in fresh milk (0.03 +/- 0.01 microg/g after storage) versus 1.1 +/- 1.0 microg/g in dissolved powder formulas and 0.2 +/- 0.3 microg/g in liquid formula. Infant formulas also contained more MDA than human milk. n-3 PUFA were more prone to oxidation than n-6 PUFA. Whether threshold levels of 4-HHE and 4-HNE would be of health concern should be elucidated.