Optimization of portable X-ray fluorescence spectrometry for the assessment of soil total copper concentrations: application at an ancient smelting site

Purpose

Copper (Cu) is the earliest anthropogenic metal pollutant, but knowledge of Cu soil concentrations at ancient metalworking sites is limited. The objective of this work was to examine the ability of portable X-ray fluorescence to quantify Cu in soils at such sites.

Materials and methods

Using a Bruker Tracer III-SD pXRF, we examine factory “scan” settings versus simple instrument parameter changes (a reduction in energy settings from 40 to 12 kV) to target analysis for Cu. We apply these to a set of uncontaminated samples (n?=?18, <?92 mg Cu kg^?1) from Central Thailand and compare results to standard wet chemistry analysis (aqua regia digestion and ICP-OES analysis). We then apply the optimized method to a set of highly contaminated samples (n?=?86, <?14,200 mg Cu kg^?1) from a known ancient smelting site.

Results and discussion

We demonstrate that simple changes to factory recommended “scan” settings can double the sensitivity of Cu determination via pXRF (“optimized limit of determination” of 19.3 mg kg^?1 versus an initial value of 39.4 mg kg^?1) and dramatically improve the accuracy of analysis. Changes to other results for other elements are variable and depend on concentration ranges, soil matrix effects, and pXRF response for the individual element. We demonstrate that pXRF can accurately determine Cu across a wide concentration range and identify grossly contaminated soil samples.

Conclusions

We conclude that pXRF is a useful tool to rapidly screen and analyse samples at remote sites and can be applied to ancient metalworking sites. Simple optimization of the pXRF settings greatly improves accuracy and is essential in determining comparative background concentrations and “unaffected” areas. Application to other elements requires further element and matrix specific optimization.

     

Intrahepatic Postsinusoidal Venous Obstruction in a Dog

Intrahepatic postsinusoidal obstruction, similar to congenital Budd-Chiari syndrome in human patients, was diagnosed in a young Basenji dog. Sonographic, radiographic, and manometric studies were used in antemortem localization of this unusual functional lesion, that was believed to be congenital.     

RADIOGRAPHIC CHARACTERISTICS OF THE FORELIMB DISTAL PHALANX AND MICROSCOPIC MORPHOLOGY OF THE LATERAL PALMAR PROCESS IN FOALS 3–32 WEEKS OLD

Developmental morphology of the forelimb distal phalanges and lateral palmar processes of 9 Thoroughbred foals aged 3–32 weeks was assessed using radiography, microradiography and histology. For inclusion in the study, all distal phalanges had no pathologic radiographic abnormalities.
Vascular channels that are characteristically found in the dorsal region of the distal phalanx were not evident radiographically in the palmar process. The proximal and distal angles of the palmar processes were separated by a lucent line continuous with the incisure in foals only through 12 weeks of age. The distal phalanges were triangular-shaped in foals 3–12 weeks of age, and were oval-shaped in older foals.
The palmar aspect of the distal phalanx was the major contributor to growth of the distal phalanx in the sagittal plane, especially between 3 and 12 weeks of age. Growth of the lateral palmar process occurred through the means of endochondral ossification. The body and cortices of the lateral palmar process were composed of coarse cancellous bone. Porosity within the lateral palmar process was greater in regions sampled axial, compared to abaxial, to the parietal sulcus and did not change with age.
A fracture was identified microradiographically and/or histologically in 9 of 18 (50%) and 10 of 17 (59%), respectively, of the lateral palmar processes examined. The fracture line was consistently associated with the parietal sulcus on the dorsal cortical surface and was always immediately abaxial to the deep digital flexor tendon attachment. No age-related morphological changes of the lateral palmar processes were identified with microradiography or histological examinations.     

Use of fetal skeletal mineralization for prediction of parturition date in cats

OBJECTIVE: To determine the relationship between parturition date and fetal skeletal mineralization detected radiographically in cats. DESIGN: Prospective clinical trial. ANIMALS: 31 queens and their 49 pregnancies. PROCEDURE: Seventeen pregnant queens were radiographed with a computed radiography system every 2 to 3 days from 1 week after pregnancy was identified by abdominal palpation until parturition. Radiographs were evaluated to determine the first identifiable mineralization of 16 bony structures and teeth during each pregnancy. This information was used to establish a table of expected parturition dates on the basis of fetal mineralization. Single radiographs from an additional 32 pregnant cats were evaluated, and predictions of parturition dates were made on the basis of the mineralization table. RESULTS: Mineralization was first detected 25 to 29 days prior to parturition (dpp). Mineralization was determined for the spinal column (22 to 27 dpp), skull (21 to 27 dpp), ribs (20 to 25 dpp), scapula (17 to 24 dpp), humerus (20 to 24 dpp), femur (19 to 23 dpp), radius (15 to 22 dpp), tibia (15 to 21 dpp), ulna (5 to 21 dpp), pelvis (8 to 20 dpp), fibula (0 to 17 dpp), tail (8 to 16 dpp), metacarpals and metatarsals (3 to 14 dpp), phalanges (0 to 11 dpp), calcaneus (0 to 10 dpp), and teeth (1 to 6 dpp). Date of parturition was predictable within 3 days in 75% of cats. CONCLUSIONS AND CLINICAL RELEVANCE: Identification of bony structures in the fetus is useful in estimating the time to parturition in queens.     

Transient and stable transfection of Chinese hamster ovary cells with the recombinant feline erythropoietin gene and expression, purification, and biological activity of feline erythropoietin protein

OBJECTIVE: To use transient and stable transfection of Chinese hamster ovary cells to clone the gene encoding feline erythropoietin (feEPO) protein, characterize the expressed protein, and assess its biological activity. SAMPLE POPULATION: Cultures of Chinese hamster ovary or TF-1 cells. PROCEDURE: The gene encoding feEPO was cloned into a eukaryotic expression plasmid. Chinese hamster ovary cells were transiently or stably transfected with the plasmid. Expressed recombinant feEPO (rfeEPO) protein was purified from transiently transfected cells. The protein was characterized by use of SDS gel electrophoresis and western blot analysis. Biological activity was assessed by measuring thymidine incorporation by TF-1 erythroleukemic cells. RESULTS: Purified rfeEPO from supernatants of transiently transfected cells was determined to be 34 to 40 kilodaltons (kd) by use of SDS gel electrophoresis, whereas the molecular weight predicted from the amino acid sequence was 21.5 kd. The banding pattern and high molecular weight suggested the protein was glycosylated. The rfeEPO proteins derived from transient or stable transfections subsequently were determined to be biologically active in vitro. CONCLUSIONS AND CLINICAL RELEVANCE: The gene encoding feEPO can be transfected into eukaryotic cells, and the expressed rfeEPO protein is biologically active in vitro. Cats with chronic renal failure often are anemic as a result of reduced expression of erythropoietin (EPO). Treatment with human-derived EPO stimulates RBCs in anemic cats; however, treatment is often limited by the development of antibodies directed against the recombinant human protein, which can then cross-react with endogenous feEPO. Recombinant feEPO may prove beneficial for use in cats with chronic renal failure.     

Gelatinase activity in synovial fluid and synovium obtained from healthy and osteoarthritic joints of dogs

OBJECTIVE: To determine matrix metalloproteinase (MMP) activity in synovial fluid (SF) obtained from the joints of dogs with degenerative joint disease (DJD) secondary to various underlying conditions. SAMPLE POPULATION: 35 samples of SF obtained from 18 clinically normal (control) dogs and 34 samples of SF obtained from 17 dogs with DJD; dogs with DJD were from 2 populations (client-owned dogs and research dogs that had DJD secondary to the lysosomal storage disease mucopolysaccharidosis VII). PROCEDURE: MMP activity in samples of SF was semiquantitatively examined by use of gelatin or casein zymography. Western blot analysis was performed by use of antibodies for MMP-2 and MMP-9. In addition, in situ MMP activity was observed in sections of synovial membrane obtained from healthy and osteoarthritic joints. RESULTS: Samples of SF from osteoarthritic joints had higher MMP-2 activity and dramatically increased MMP-9 activity, compared with values for healthy joints. Substrate-overlay analyses indicated minimal gelatin-degrading activity in synoviocytes obtained from control dogs, whereas greater activity was seen in osteoarthritic synoviocytes, with additional activity in the underlying tissue. CONCLUSIONS AND CLINICAL RELEVANCE: Higher MMP-2 activity and dramatic increases in MMP-9 activity were associated with the osteoarthritic state, even though MMP-2 activity was detected in healthy joints. This study expands information on MMP production in SF of osteoarthritic joints in other species and documents the similarity of MMP activity patterns regardless of the cause of DJD.