Cadmium content of wheat grain from a long-term field experiment with sewage sludge

Grain Cd concentrations were determined in the wheat (Triticum aestivum L.) cultivars Soissons, Brigadier, and Hereward grown in 1994,1996, and 1999, respectively, in soils of a long-term field experiment to which sewage sludges contaminated with Zn, Cu, Ni, or Cr had previously been added. Soil pore water soluble Cd and free Cd2+ increased linearly with increasing total soil Cd (R2=0.82 and 0.84, respectively; P<0.001). Similarly, soil pore water free Cd2+ increased linearly with increasing soil pore water soluble Cd (R2=0.98; P<0.001). There was no evidence of a plateau in soil pore water Cd concentrations with increasing soil Cd concentrations. Grain Cd concentrations were significantly correlated with total soil Cd (P<0.001), soil pore water Cd (P<0.001), and free Cd2+ (P<0.001). A slight curvilinear relationship between grain Cd and soil Cd was apparent, but there was no plateau, even at the maximum soil Cd concentration of about 2.7 mg kg(-1). The relationship between soil pore water Cd and grain Cd was linear for all three cultivars. The slopes were in the order 1994 > 1996 > 1999, with more Cd being taken up into the grain by Soissons grown in 1994, and least by Hereward grown in 1999. For Soissons, Cd concentration in the grain greater than the EU limit (0.24 mg kg(-1) dry wt.) occurred at soil Cd less than the current UK limit of 3 mg kg(-1) for soils receiving sewage sludge. In contrast, for Brigadier and Hereward, grain Cd concentrations were near to and less than the EU limit, respectively, at soil Cd concentrations of 3 mg kg(-1).     

环境中的药物——LC-MS/MS分析地表水和地下水

成百上千的活性物质正被用于人药和兽药处方中.由于药物的广泛应用,它们的残留物可通过多种途径进入环境.虽然主要通过尿和粪便的排泄,但是药品生产中的排放也应被考虑.当抗生素用于水产业,就会产生更直接的影响.污水处理设备不能完全除去药物,因此药物会出现在地表和地下水样品中.近年来,人们对环境中药物的兴趣正在增加,需要建立一种快速、灵敏、有选择性的方法来分析水样.     

Factors affecting the concentrations of lead in British wheat and barley grain

The entry of Pb into the food chain is of concern as it can cause chronic health problems. The concentration of Pb was determined in cereal grain samples collected representatively from British Cereal Quality Surveys in 1982 and 1998 (n = 176, 250 and 233 for wheat collected in 1982 and 1998, and barley in 1998, respectively). In addition, paired soil and grain samples were collected from 377 sites harvested across Britain in 1998-2000. Wheat grain Pb ranged from below the analytical detection limit (0.02 mg kg(-1) dry weight, DW) to 1.63 mg kg(-1) DW, and barley grain Pb from <0.02 to 0.48 mg kg(-1) DW. The vast majority of samples (>99% for both wheat and barley, excluding Scottish barley samples collected in 2000) were well below the newly introduced EU limit for the maximum permissible concentration of Pb in cereals (0.2 mg kg(-1) fresh weight, equivalent to 0.235 mg kg(-1) DW). There was a significant reduction in wheat grain Pb in the 1998 survey compared with the 1982 survey. However, 40 barley samples collected from Scotland in 2000 in the paired soil and crop survey showed anomalously high concentrations of Pb, with 10 samples exceeding the EU limit. Washing experiments demonstrated that surface contamination, introduced during grain harvest and/or storage, was the main reason for the high concentrations in these samples. In the paired soil and crop surveys, there were no significant correlations between grain Pb concentrations with total soil Pb and other soil properties, indicating low bioavailability of Pb in the soils and limited uptake and transport of Pb to grain. The Pb in cereal grain is likely to originate mainly from atmospheric deposition and other routes of surface contamination during harvest and storage.     

Determination of chemical availability of cadmium and zinc in soils using inert soil moisture samplers

A rapid method for extracting soil solutions using porous plastic soil-moisture samplers was combined with a cation resin equilibration based speciation technique to look at the chemical availability of metals in soil. Industrially polluted, metal sulphate amended and sewage sludge treated soils were used in our study. Cadmium sulphate amended and industrially contaminated soils all had > 65% of the total soil solution Cd present as free Cd2+. However, increasing total soil Cd concentrations by adding CdSO4 resulted in smaller total soil solution Cd. Consequently, the free Cd2+ concentrations in soil solutions extracted from these soils were smaller than in the same soil contaminated by sewage sludge addition. Amendment with ZnSO4 gave much greater concentrations of free Zn2+ in soil solutions compared with the same soil after long-term Zn contamination via sewage sludge additions. Our results demonstrate the difficulty in comparing total soil solution and free metal ion concentrations for soils from different areas with different physiochemical properties and sources of contamination. However, when comparing the same Woburn soil, Cd was much less available as Cd2+ in soil solution from the CdSO4 amended soils compared with soil contaminated by about 36 years of sewage sludge additions. In contrast, much more Zn was available in soil solution as free Zn2+ in the ZnSO4 amended soils compared with the sewage sludge treated soils.     

Speciation of zinc in contaminated soils

The chemical speciation of zinc in soil solutions is critical to the understanding of its bioavailability and potential toxic effects. We studied the speciation of Zn in soil solution extracts from 66 contaminated soils representative of a wide range of field conditions in both North America and Europe. Within this dataset, we evaluated the links among the dissolved concentrations of zinc and the speciation of Zn(2+), soil solution pH, total soil Zn, dissolved organic matter (DOM), soil organic matter (SOM) and the concentrations of different inorganic anions. The solid-liquid partitioning coefficient (K(d)) for Zn ranged from 17 to 13,100Lkg(-1) soil. The fraction of dissolved Zn bound to DOM varied from 60% to 98% and the soil solution free Zn(2+) varied from 40% to 60% of the labile Zn. Multiple regression equations to predict free Zn(2+), dissolved Zn and the solid-liquid partitioning of Zn are given for potential use in environmental fate modeling and risk assessment. The multiple regressions also highlight some of the most important soil properties controlling the solubility and chemical speciation of zinc in contaminated soils.     

Soil solid-phase controls lead activity in soil solution

Lead pollution of the environment is synonymous with civilization. It has no known biological function, and is naturally present in soil, but its presence in food crops is deemed undesirable. The concern regarding Pb is mostly due to chronic human and animal health effects, rather then phytotoxicity. However, not much is known about the chemistry and speciation of Pb in soils. We determined the activity of Pb2+, in near neutral and alkaline soils, representative of alluvial, desertic and calcareous soils of Egypt, using the competitive chelation method. Lead activity ranged from 10(-6.73) to 10(-4.83) M, and was negatively correlated with soil and soil solution pH (R2 = -0.92, P < 0.01 and R2 = -0.89, P < 0.01, respectively). It could be predicted in soil solution from the equation: log(Pb2+) = 9.9 - 2pH. A solubility diagram for the various Pb minerals found in soil was constructed using published thermodynamic data obtained from the literature, and our measured Pb2+ activities compared with this information. The measured Pb2+ activities were undersaturated with regard to the solubility of PbSiO3 in equilibrium with SiO2 (soil). However, they were supersaturated with regard to the solubilities of the Pb carbonate minerals PbCO3 (cerussite) and Pb3(CO3)2(OH)2 in equilibrium with atmospheric CO2 and hydroxide Pb(OH)2. They were also supersaturated with regard to the solubilities of the Pb phosphate minerals Pb3(PO4)2, Pb5(PO4)3OH, and Pb4O(PO4)2 in equilibrium with tricalcium phosphate and CaCO3. The activity of Pb2+ was not regulated by any mineral of known solubility in our soils, but possibly by a mixture of Pb carbonate and phosphate minerals.     

Cross-sectional biomonitoring study of pesticide exposures in Queensland,Australia, using pooled urine samples

A range of pesticides are available in Australia for use in agricultural and domestic settings to control pests, including organophosphate and pyrethroid insecticides, herbicides, and insect repellents, such as N,N-diethyl-meta-toluamide (DEET). The aim of this study was to provide a cost-effective preliminary assessment of background exposure to a range of pesticides among a convenience sample of Australian residents. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n = 24 pools of 100 specimens). Concentrations of urinary pesticide biomarkers were quantified using solid-phase extraction coupled with isotope dilution high-performance liquid chromatography–tandem mass spectrometry. Geometric mean biomarker concentrations ranged from <0.1 to 36.8 ng/mL for organophosphate insecticides, <0.1 to 5.5 ng/mL for pyrethroid insecticides, and <0.1 to 8.51 ng/mL for all other biomarkers with the exception of the DEET metabolite 3-diethylcarbamoyl benzoic acid (4.23 to 850 ng/mL). We observed no association between age and concentration for most biomarkers measured but noted a “U-shaped” trend for five organophosphate metabolites, with the highest concentrations observed in the youngest and oldest age strata, perhaps related to age-specific differences in behavior or physiology. The fact that concentrations of specific and non-specific metabolites of the organophosphate insecticide chlorpyrifos were higher than reported in USA and Canada may relate to differences in registered applications among countries. Additional biomonitoring programs of the general population and focusing on vulnerable populations would improve the exposure assessment and the monitoring of temporal exposure trends as usage patterns of pesticide products in Australia change over time.     

Cadmium availability to wheat grain in soils treated with sewage sludge or metal salts

Grain Cd concentrations were determined in wheat (Triticum aestivum L.) grown in 1999, 2001 and 2003, at six sludge cake field experiments. Three of these sites also had comparisons with Cd availability from metal amended liquid sludge and metal salts. Grain Cd concentrations in all years and at all sites were significantly linearly correlated with NH4NO3 extractable Cd and soil total Cd (P<0.001). Soil extractability was greater in the liquid sludge and metal salt experiments than in the cake experiments, as were grain Cd concentrations. Across all the sites, NH4NO3 extractable soil Cd was no better at predicting grain Cd than soil total Cd. Stepwise multiple linear regression analysis showed that soil total Cd, pH and organic carbon were the only significant (P<0.001) variables influencing wheat grain Cd concentrations, explaining 78% of the variance across all field experiments (1408 plots). This regression predicted that the current UK soil total Cd limit of 3 mg kg(-1) was not sufficiently protective against producing grain above the European Union (EU) grain Cd Maximum Permissible Concentration (MPC) of 0.235 mg Cd kg(-1) dry weight, unless the soil pH was > 6.8. Our predictions show that grain would be below the MPC with > 95% confidence with the proposed new EU draft regulations permitting maximum total Cd concentrations in soils receiving sludge of 0.5 mg kg(-1) for soils of pH 5-6, 1 mg kg(-1) for soils of pH 6-7, and 1.5 mg kg(-1) for soils of pH > or = 7.