Heavy Metals Contamination in Vegetables Grown in Urban and Metal Smelter Contaminated Sites in Australia

Dietary exposure to heavy metals, namely cadmium (Cd), lead (Pb), zinc (Zn) and copper (Cu), has been identified as a risk to human health through the consumption of vegetable crops. This study investigates the source and magnitude of heavy metal contamination in soil and vegetable samples at 46 sites across four vegetable growing regions in New South Wales, Australia. The four regions Boolaroo, Port Kembla, Cowra and the Sydney Basin were a mix of commercial and residential vegetable growing areas. The extent of metal contamination in soils sampled was greatest in regions located in the vicinity of smelters, such as in Boolaroo and Port Kembla. Soil metal concentrations decreased with depth at these two sites, suggesting contamination due to anthropogenic activities. Cadmium, Pb and Zn contamination was greatest in vegetables from Boolaroo, and Cu concentrations were greatest in vegetables sampled from Port Kembla. At Boolaroo, nearly all the samples exceeded the Australian Food Standards maximum level (ML) (0.01 mg kg^?1 fresh weight) of Cd and Pb in vegetables. Over 63% of samples exceeded international food standard guidelines set by the Commission of the European Communities and the Codex Alimentarius Commission. All vegetables sampled from Cowra, which is a relatively pristine site had Cd and Pb levels below the Australian and international food standards guideline values. This study suggests that the Australian guideline values are more conservative in defining the ML for Cd and Pb in vegetable crops. This investigation highlights the increased danger of growing vegetables in the vicinity of smelters.     

Degradation of isoxaflutole (balance) herbicide by hypochlorite in tap water

Chlorine has been widely employed for the disinfection of drinking water. Additionally, it has the capacity to oxidize many organic compounds in water. Isoxaflutole (Balance; IXF) belongs to a new class of isoxazole herbicides. Isoxaflutole has a very short soil half-life and rapidly degrades to a stable and phytotoxic metabolite, diketonitrile (DKN). Further degradation of DKN produces a nonbiologically active benzoic acid (BA) metabolite. In experiments using high-performance liquid chromatography-UV spectroscopy (HPLC-UV) and HPLC tandem mass spectrometry (HPLC-MS/MS), DKN was found to rapidly react with hypochlorite in tap water, yielding the BA metabolite as the major end product. One milligram per liter (19 microM) of hypochlorite residue in tap water was able to completely oxidize up to 1600 microg/L (4.45 micromol/L) of DKN. In tap water, the disappearance of IXF was much more rapid than in DI water. As soon as the IXF is hydrolyzed to DKN, the DKN quickly reacts with the OCl(-) to form nonphytotoxic BA. As a result, the herbicide solutions prepared with tap water at 500 microg/L will no longer possess any herbicidal activity after 48 h of storage. However, in agronomic settings, highly concentrated tank solutions (600-800 mg/L) may be prepared with tap water since the conversion of IXF to BA would represent <5% of the herbicide; therefore, any impact on the herbicide efficacy would be negligible. Results of this study show that current chlorination disinfection protocols in municipal water systems would completely eliminate the phytotoxic form of this new herbicide, DKN, from drinking water supplies; yet, farmers can use chlorinated tap water without significant loss of efficacy.     

Spectrophotometric methods to determine carbohydrates in soil

Two common spectrophotometric procedures for determining neutral carbohydrates—the phenol-sulfuric acid and anthrone methods were evaluated for soil analysis. The phenol-sulfuric acid procedure gives results comparable to those obtained by gas-liquid chromatography, and is applicable to a variety of soil types. Prior removal of interfering substances by anion and cation exchange is required. Glucose is recommended as the spectrophotometric reference standard. The anthrone method is not satisfactory under the conditions employed.     

Techniques for air pollution observation from space

Air pollution problems of a scale larger than the point monitoring problem lend themselves to space observational techniques. Examples of these large scale problems are those associated with changes in the global background of gases and aerosols; potential stratospheric pollution resulting from SST operations; regional sources, pollution episodes, and large scale diffusion; and effects of pollutants on climate. These problems are discussed and observational requirements are specified. Possible remote sensing techniques for satellite monitoring are described. These include monitoring of pollutant gases and particulates by means of their absorption and scattering of radiation in both the solar spectrum range and terrestrial emission spectrum range. A discussion of potential difficulties includes the atmospheric and surface background problems, the temperature sensitivity problem in the terrestrial spectrum range, the band overlap problem, and the cloud interference problem. Recent observations from satellites and balloons are reviewed. It appears that except for H₂O, and, perhaps, O₃, measurements of the vertical profiles of atmospheric pollutant gases and aerosols from satellites will be extremely difficult. On the other hand, measurements of the total amounts (in a vertical column) of pollutant gases and aerosols do appear feasible.     

Determination of isoxaflutole (balance) and its metabolites in water using solid phase extraction followed by high-performance liquid chromatography with ultraviolet or mass spectrometry

Balance (isoxaflutole, IXF) belongs to a new family of herbicides referred to as isoxazoles. IXF has a very short soil half-life (<24 h), degrading to a biologically active diketonitrile (DKN) metabolite that is more polar and considerably more stable. Further degradation of the DKN metabolite produces a nonbiologically active benzoic acid (BA) metabolite. Analytical methods using solid phase extraction followed by high-performance liquid chromatography-UV (HPLC-UV) or high-performance liquid chromatography-mass spectrometry (HPLC-MS) were developed for the analysis of IXF and its metabolites in distilled deionized water and ground water samples. To successfully detect and quantify the BA metabolite by HPLC-UV from ground water samples, a sequential elution scheme was necessary. Using HPLC-UV, the mean recoveries from sequential elution of the parent and its two metabolites from fortified ground water samples ranged from 68.6 to 101.4%. For HPLC-MS, solid phase extraction of ground water samples was performed using a polystyrene divinylbenzene polymer resin. The mean HPLC-MS recoveries of the three compounds from ground water samples spiked at 0.05-2 microg/L ranged from 100.9 to 110.3%. The limits of quantitation for HPLC-UV are approximately 150 ng/L for IXF, 100 ng/L for DKN, and 250 ng/L for BA. The limit of quantitation by HPLC-MS is 50 ng/L for each compound. The methods developed in this work can be applied to determine the transport and fate of Balance in the environment.     

Effect of dietary dried tomato pulp on oxidative stability of Japanese quail meat

Ninety, 21-day-old, Japanese quail (Coturnix coturnix japonica) divided into three groups with five subgroups each were fed a basal diet that served as control or a basal diet containing 5 or 10% of dried tomato pulp (DTP), a byproduct of the tomato-processing industry. The DTP contained lycopene and beta-carotene at 281 and 24.3 mg kg(-)(1) of dry weight, respectively. On day 42 of age, birds were slaughtered, and carcasses were trimmed for breast meat. To assess the effect of dietary treatment on the oxidative stability of raw and cooked meat, raw meat was subjected to iron-induced lipid oxidation, whereas both raw and cooked meats were subjected to refrigerated storage at 4 degrees C. The extent of lipid oxidation was determined on the basis of the malondialdehyde (MDA) formed through the use of third-order derivative spectrophotometry. Results showed that after 6 and 9 days of refrigerated storage, MDA values in raw meat were increased. The increase was higher (P < 0.05) for the 10% DTP group and lower (P < 0.05) for the 5% DTP group, compared to control. An analogous oxidation profile was observed for cooked meat at 3, 6, and 9 days of storage. Iron-induced lipid oxidation of raw meat showed that the 10% DTP group as well as the control group exhibited MDA values that did not differ (P > 0.05) from each other at all time points, whereas the 5% DTP group presented MDA values that, although not differing from those of the other groups at 0 and 50 min, were significantly (P < 0.05) lower than those of the other groups at 100 and 150 min of iron-induced lipid oxidation. These results suggested that inclusion of dried tomato pulp in feed at a level of 5% exerted an antioxidant effect, whereas addition at level of 10% exerted a prooxidant effect. Mean alpha-tocopherol levels in the control, 5% DTP, and 10% DTP groups were 2.2, 2.1, and 1.4 mg kg(-)(1) of meat, respectively. Fatty acid analysis showed that the 10% DTP group had a higher (P < 0.05) content of total polyunsaturated fatty acids and a greater (P < 0.05) unsaturated/saturated fatty acid ratio compared to control. There might be an interaction between DTP and alpha-tocopherol that is of importance for the balance between pro- and antioxidative activities. Future experiments should be designed to explore the interaction between individual carotenoids and tocopherols in order to better elucidate their role in oxidative changes.     

Oxidation and Removal of 1,2,4-Trichlorobenzene using Sodium Persulfate in a Sorption-Desorption Experiment

Peat soils with a gradient of naturally high Cd and Zn (up to 190 and 70,000,mg/kg, respectively) were sampled at several depths from a wetland overlying Zn-rich dolomitic bedrock. Total concentrations of Zn, Cd and S were generally much higher in the seasonally water-saturated subsoils than at the surface. Leaching studies with intact soil columns showed the subsoils generally have a greater tendency to release Zn, Cd and S than the topsoils. Zn and Cd leaching were correlated to sulfate dissolution, with 6 successive leaching events removing up to 4% and 13% of the total Zn and S, respectively, from the most metal-rich subsoils. Relative leaching losses were less from the surface soils, not exceeding 1% and 3% of total Zn and S. Because Zn was relatively more soluble and extractable by 0.01,M CaCl₂ than Cd, Zn/Cd ratios in column leachates and field-sampled groundwater were higher than the soil Zn/Cd ratios. Consequently, the potential for loss of Zn from the soil by leaching was higher than that of Cd, particularly from the subsoil. Nevertheless, some soil layers of the profile were enriched in total Zn relative to Cd, indicated by Zn/Cd ratios well above that of the Cd-rich sphalerite in the parent dolomitic rock. This enrichment may be explained by historical migration and re-immobilization of Zn as sulfides. The low solubility of Cd in the peats despite high total Cd suggests preferential immobilization of this metal by organic sulfur or sulfide.     

Determination of oryzalin in water, citrus fruits, and stone fruits by liquid chromatography with tandem mass spectrometry

A new methodology is described for rapidly determining the herbicide oryzalin in water, citrus fruits, and stone fruits by liquid chromatography with negative ion electrospray ionization tandem mass spectrometry (LC/MS/MS). Oryzalin is extracted from water using a polymeric sorbent solid phase extraction (SPE) column and from fruit using methanol. The water samples require no further purification, but an aliquot of the fruit sample extracts is diluted with water and purified using a polymeric 96 well SPE plate. Purified extracts are concentrated prior to determination by LC/MS/MS at m/z 345 (Q1) and m/z 281 (Q3) using an external standard for calibration. The validated limits of quantitation were 0.05 microg/L in water (drinking water, surface water, and groundwater) and 0.01 microg/g in citrus fruits (oranges and lemons) and stone fruits (peaches and cherries). Recoveries averaged 102% for water samples and 85-89% for the various types of fruit samples. For all fortification levels combined, the relative standard deviations ranged from 4 to 6% for water and from 2 to 4% for fruit.     

Carbohydrate composition of selected plum/prune preparations

Eighteen plum/prune preparations and byproducts were analyzed for proximate constituents and carbohydrate profiles. Plum puree and prune juice contained the highest concentrations of ash (13.0 and 13.8%, respectively). Crude protein (CP), acid-hydrolyzed fat (AHF), and total dietary fiber (TDF) concentrations were higher in byproducts (waste cake and dried plum pits) compared with the other fractions. Several classes of oligosaccharides were found in low concentrations in many of the substrates and were associated with the fruit rather than the pit. Maltooligosaccharides were found in very high concentrations in three of the preparations as a result of the addition of maltodextrin during processing. Monosaccharides, sugar alcohols, and oligosaccharides were found in higher concentrations in the fruit than in the pit and accounted for 2.9-84.7% of substrate organic matter. These results indicate that carbohydrates of various types constitute a significant proportion of plum/prune preparations and byproducts.