An alternative approach for assessment of liquid chromatography-mass spectrometry matrix effects using auto-sampler programmed co-injection.

We report the use of auto-sampler programmable functions to co-inject analyte standard solution and matrix extract to assess ion enhancement and suppression (matrix effects) in LC-MS. This is effectively an automated post-extraction addition (APEA) procedure, emulating the manual post-extraction addition (PEA) approach widely adopted for assessment of matrix effects. To verify that APEA was comparable to the conventional PEA approach, matrix effects were determined using both methods for a selection of 31 illicit and pharmaceutical drugs in 10 different human urine extracts. Matrix effects measured using APEA were statistically indistinguishable from manual PEA methodology for 27 of the 31 drugs. Of the four drugs that showed significant differences using the two methods, three differed by less than 2 %, which is within the expected accuracy limits required for matrix effect determinations. The remaining analyte, trimeprazine, was found to degrade in the spiked PEA matrix extract, accounting for the difference between matrix effects measured by the PEA and APEA approaches. APEA enables a single matrix extract to be assessed at multiple analyte concentrations, resulting in a considerable reduction in sample preparation time. In addition, APEA can reduce the quantity of analyte-free sample matrix required for matrix effect assessment, which is an important consideration in certain analytical and bioanalytical fields. This work shows that APEA may be considered as an acceptable alternative to PEA for the assessment of matrix effects in LC-MS method validation and may be applicable to a variety of matrices such as environmental samples.

Behaviour of fullerenes (C60) in the terrestrial environment: potential release from biosolids-amended soils.

Owing of their wide-range of commercial applications, fullerene (C60) nanoparticles, are likely to reach environments through the application of treated sludge (biosolids) from wastewater treatment plants to soils. We examined the release behaviour of C60 from contaminated biosolids added to soils with varying physicochemical characteristics. Incubation studies were carried out in the dark for up to 24 weeks, by adding biosolids spiked (1.5mg/kg) with three forms of C60 (suspended in water, in humic acid, and precipitated/particulate) to six contrasting soils. Leaching of different biosolids+soil systems showed that only small fractions of C60 (<5% of applied amount) were released, depending on incubation time and soil properties (particularly dissolved organic carbon content). Release of C60 from unamended soils was greater (at least twice as much) than from biosolids-amended soils. The form of C60 used to spike the biosolids had no significant effect on the release of C60 from the different systems. Contact time of C60 in these systems only slightly increased the apparent release up to 8 weeks, followed by a decrease to 24 weeks. Mass balance analysis at the completion of the experiment revealed that 20-60% of the initial C60 applied could not be accounted for in these systems; the reasons for this are discussed.

Marked changes in herbicide sorption-desorption upon ageing of biochars in soil.

We studied the sorption-desorption behaviour of two herbicides (diuron and artrazine) in a soil rich in Fe and Al oxides (Ferrosol), either amended freshly with two different types of biochars or that contained biochars aged under field conditions. Standard batch sorption-desorption experiments were conducted on soil samples freshly amended with two biochars, (namely, poultry litter - PL and paper mill - PM sludge) as well on those collected from field 32 months after biochar application. Soils that were freshly amended with biochars @ 10 t ha(-1) showed a two (PM) to five (PL) fold increase in sorption of herbicides as compared with that in the unamended soil. For example, the fresh amendments with PL biochar at 10 t ha(-1) led to a highly significant (P<0.001) increase in the Freundlich sorption coefficient (K(f)) of atrazine; i.e. 20.71 (n=0.40) as compared with 4.02 (n=0.70) for the control soil. Sorption was reversible in the unamended soil but sorption-desorption hysteresis was prominent in the soil amended with fresh biochars. In contrast, the soil containing aged biochars (at 10 t ha(-1)) exhibited sorption-desorption properties that were statistically similar to that of the control soil, especially for atrazine. Ageing of biochars in the soil over a 32 months period reduced the sorption capacity by 47% (PM) to 68% (PL) for diuron. These findings may have implications for herbicide efficacy in biochar amended soils.