Tracing Pharmaceuticals in the Unsaturated Zone (10 pp)

Background, Aim and Scope   One of the first occurrences of pharmaceutically active compounds in groundwater was reported from the sewage irrigation farms south of Berlin. At these sewage irrigation farms treated sewage effluent passed the soil and unsaturated zone before reaching the aquifer. Clofibric acid was detected in pore water from soils of those sewage irrigation farms in concentrations between 65 ng/L and 1430 ng/L. The aim of this study was to investigate the transport behavior of regularly detected clofibric acid, diclofenac, ibuprofen, and propyphenazone under conditions comparable to those at the sewage irrigation farms in a multiple compound sand column laboratory experiment. Materials and Methods   Sediment column experiments were conducted to study the transport of pharmaceuticals in the unsaturated zone. The migration was measured in fine to medium grained sand and leaching solution containing 1 mg/L of pharmaceutically active compounds and 61 mg/L of the tracer lithium chloride (LiCl). For the analysis of the pharmaceutical compounds the water samples were adjusted to a pH value of 2 and then extracted by solid-phase extraction (SPE). Before extraction, the samples were spiked with a surrogate standard for analytical quality control. The sample extracts were analyzed by capillary gas chromatography-mass spectrometry (GC-MS) with selected ion monitoring (SIM). Depending on the sample volume (100 to 200 mL) and the matrix, the limits of detection were between 1 and 10 ng/L, and the limits of quantitation were between 5 and 25 ng/L. Analysis for calcium, magnesium and lithium were carried out using a 'Trace Scan' ICP-AES from Thermo Jarrel Ash. Sodium, potassium, iron and manganese were analyzed using a Philips PU 9400 flame AAS. Analysis of anions was performed on a Dionex ion chromatograph DX 120. Results   At the sewage irrigation farms the average concentrations of clofibric acid in the unsaturated zone declined from higher values near ground surface (480 ng/L) to lower values near the groundwater table (65 ng/L). From the pharmaceuticals analyzed only clofibric acid, primidone and propyphenazone could be analyzed in the first (upper) aquifer at the sewage irrigation farms. All other pharmaceuticals could neither be detected in the first aquifer nor in the deeper aquifers. Breakthrough curves from soil column experiments revealed no transformation and no retardation for clofibric acid, whereas transformation of diclofenac was so high (79%) that no retardation factor could be calculated. Ibuprofen was significantly transformed (37%), transformation of propyphenazone (17%) was quite low and retardation (Rf = 2.05) was in the range of previously conducted column experiments. Discussion   The results confirm previously conducted experiments with clofibric acid where this compound was identified as highly mobile and persistent. The results that diclofenac and ibuprofen are significantly transformed where unexpected as other studies exhibited much lower transformation under saturated conditions at least for diclofenac. However, lower pH values and higher oxygen contents in the unsaturated zone compared to the aquifer may explain this observed high transformation of these compounds at the column experiments. Conclusions   We conclude that irrigation with sewage effluent containing the compounds used in our experiments will lead to an input into groundwater of clofibric acid, whereas diclofenac and ibuprofen will most likely be transformed during the passage. Propyphenazone will be retarded but will most likely occur in groundwater. These results from the column experiments coincide very well with the occurrence of the pharmaceuticals clofibric acid, primidone, and propyphenazone in the first aquifer. Recommendations and Perspective  : The results underline the need to study the sorption of pharmaceuticals on various materials. e.g. organic matter, surfaces at pH values occurring in the unsaturated zone. Future field studies will also include the investigation of desorption behavior in the unsaturated zone.     

Fatty acids and fat-soluble vitamins in salted herring (Clupea harengus) products

The fatty acid composition and contents of fat and fat-soluble vitamins of three salted products prepared from Icelandic herring were analyzed. The effects of storage on the products over their shelf life, 6 or 12 months, were investigated. The average oil content of salted, gutted herring and salted fillets in vacuum remained constant, 17 and 12% of wet weight, respectively. In the pickled product the oil content decreased during the 12 months of storage from 13 to 12%. The composition of the products was typical for herring, the most abundant fatty acids being oleic (18:1n-9), palmitic (16:0), cetoleic (22:1n-11), and gadoleic (20:1n-9) acids. Monounsaturated acids constituted clearly the main group with a proportion of >50% of all fatty acids. Eicosapentaenoic acid (EPA, 20:5n-3) and docosahexaenoic acid (DHA, 22:6n-3) comprised together >12% of all fatty acids. During storage, some hydrolysis of triacylglycerol (TAG) occurred, causing a slight reduction in practically all esterified fatty acids. In none of the three products was the loss of polyunsaturated fatty acids from TAG greater than the loss of saturated ones, indicating that the loss of EPA and DHA was not due to oxidation. After packing, the average content of vitamins A, D, and E in the products varied between 27 and 87 microg/100 g (wet weight), between 17-28 microg/100 g (wet weight), and between 77-120 microg/100 g (wet weight), respectively. During storage, the level of vitamin A decreased significantly, whereas no loss of vitamin D was observed. The content of vitamin E was low in all products and showed wide variation. When compared to the recommended daily intake, it could be concluded that the products investigated were good and stable sources of long-chain n-3 fatty acids (EPA, DHA) and vitamin D.     

Effect of drying and rewetting on phosphorus transformations in red brown soils with different soil organic matter content

In this study, the effect of drying and rewetting on native P transformations in two red brown soils with different management history was investigated. Three treatments, T1 (constantly moist), T2 (dried for 4 days and then kept dry), T3 (rewetted after 4 days drying) were used. Drying and rewetting caused a rapid increase in microbial P (Pm) and labile organic P (labile Po) within 1 day and a gradual increase in available inorganic P (Colwell). These increases were only temporarily, as Pm and labile Po decreased with time and were at the same level as in the constantly moist soil by the end of the incubation period of 21 days. The effect of drying and rewetting on P transformations strongly depended on soil organic matter content, being more pronounced in the soil with high organic matter content, compared to the soil with low soil organic matter content.     

The impact of high speed, high volume traffic axes on brown bears in Slovenia

The Ljubljana-Razdrto highway and the parallel Ljubljana-Trieste railway cut through critical brown bear (Ursus arctos) habitat in south-central Slovenia. These high speed, high volume traffic axes are located close to the main dispersal corridor for bears from the Dinaric Mountain range into the Alps. We analyzed radiotracking data of 15 individual bears that lived within 10 km of the highway, compared transportation related and overall known bear mortality, and analyzed the spatial distribution of bear-vehicle accidents. The highway posed a home range boundary to resident bears, but was not an absolute barrier. Transportation-related mortality was high in the vicinity of the highway and railway, and averaged 31% of the total known local mortality from 1992 to 1999. At present the detrimental impact of transportation routes on the bear population in Slovenia is modest due to the high density of bears and the low density of highways—but new highways are planned or already under construction. Managers have to be aware that, due to bears large home ranges and long dispersal distances, a single highway affects bears from a huge area—emphasizing the importance of international cooperation and a landscape approach in highway planning.     

Growth,P uptake and rhizosphere properties of wheat and canola genotypes in an alkaline soil with low P availability

The aim of the present study was to assess the role of soil type on growth, P uptake and rhizosphere properties of wheat and canola genotypes in an alkaline soil with low P availability. Two wheat (Goldmark and Janz) and two canola genotypes (Drum and Outback) were grown in a calcareous soil (pH 8.5) at two P levels [no P addition (0P) or addition of 200 mg kg⁻¹ P as Ca₃(PO₄)₂ (200P)] and harvested at flowering or maturity. Shoot and root dry weight, root length and shoot P content were greater in the two canola genotypes than in wheat. There were no consistent differences in available P, microbial P and phosphatase activity in the rhizosphere of the different genotypes. Shoot P content was significantly positively correlated with root length, pH and phosphatase activity in the rhizosphere. The microbial community composition, assessed by fatty acid methylester analysis, of the canola genotypes differed strongly from that of the wheat genotypes. The weight percentage bacterial fatty acids, the bacteria/fungi (b/f) ratio and the diversity of fatty acids were greater in the rhizosphere of the canolas than in the rhizosphere of the wheat genotypes. In contrast to the earlier studies in an acidic soil, only small differences in growth and P uptake between the genotypes of one crop were detected in the alkaline soil used here. The results confirmed the importance of root length for P uptake in soils with low P availability and suggest that the rhizosphere microbial community composition may play a role in the better growth of the canola compared to the wheat genotypes.     

Boric acid as alternative reference substance for earthworm field tests

Purpose  

Boric acid was applied in an earthworm field test according to ISO 11268-3 as a possible alternative for the currently used reference substances that may no longer be available in the near future.     

A gamma‐ray spectrometry approach to field separation of illuviation‐type WRB reference soil groups in northern Thailand

According to the World Reference Base for Soil Resources (IUSS Working Group WRB, 2006), the differentiation of Acrisols and Alisols is based on the cation‐exchange capacity of clay, which cannot be directly determined in the field, but needs expensive and time‐consuming soil‐chemical analyses. This is an unsatisfactory situation for pedologists, who urgently require a rapid field method to distinguish illuviation‐type reference soil groups (Alisols, Acrisols, Luvisols, Lixisols). In this study, we tested the ability of gamma‐ray spectrometry to separate major WRB reference soil groups in the field. The underlying hypothesis is that Alisols and Acrisols are distinguished by their clay mineral composition, which should be reflected by geochemistry and consequently gamma‐ray radiation (i.e., K‐containing illite vs. K‐free kaolinite). Highly significant differences in their gamma‐ray spectrum for K, Th, and U were found for limestone and its soils. Especially the K and Th signatures allowed a clear separation of Acrisols and Alisols. In general, the surface radiation was sufficient to separate these soils. Best results were revealed considering parent rock and the whole soil profile. This means by using a portable radiometer and a pH meter, all illuviation‐type reference soil groups could be distinguished in this case. If applicable at other sites, this approach could enormously reduce expenditures for soil‐chemical analysis needed to assist soil classification.     

Detection of phloridzin in strawberries (Fragaria x ananassa Duch.) by HPLC-PDA-MS/MS and NMR spectroscopy

The phenolic profile of strawberry fruits (Fragaria x ananassa Duch., Rosaceae) was investigated by high-performance liquid chromatography with photodiode array detection. A peak displaying retention time and UV spectral data identical to those of phloridzin (phloretin 2'-O-beta-d-glucoside), a dihydrochalcone glucoside so far considered characteristic of apples, was monitored. For further characterization, crude extracts of strawberries were purified on polyamide, and the target compound was isolated by preparative and analytical HPLC. Structure elucidation was performed on the basis of APCI- and ESI-MS in the negative ion mode as well as by 1D and 2D NMR spectroscopy using authentic phloridzin for comparison. The d-configuration of the sugar moiety was established by HPLC analysis of the corresponding acyclic 1-deoxy-1-(N-acetyl-alpha-methylbenzylamino)alditol acetate. Apart from its chemotaxonomic relevance, this first report on the occurrence of phloridzin in strawberries is of particular interest for the authenticity control of strawberry products such as juices, jams, and fruit preparations since phloridzin has so far been used for the detection of fraudulent admixtures.     

Previous water content influences the response of soil respiration to changes in water content in non-saline and saline soils

Three incubation experiments were carried out with a non-saline soil (electrical conductivity in a saturation paste (ECe) 1 dS m^?1) to which NaCl was added to achieve ECe 10 and 30 dS m^?1; pea straw was added at 20 g kg^?1 as a nutrient source. Experiment 1 showed that cumulative respiration was highest in soil EC 1 and lowest in soil EC 30. The optimal water content for respiration was 60–70 % of WHC in all soils. There were two periods (days 1–7 and days 8–17) in Experiment 2. In the treatments with the same water content in both periods [optimal (O-O) and medium (M-M)], respiration rates decreased over time and were lower in M-M than in O-O. Cumulative respiration at medium water content did not differ between slow (L-SM) or rapid rewetting (L-RM) from low to medium water content. There were two periods in Experiment 3 with the water content in the first period 50, 40 or 30 % of WHC adjusted from 60 % during pre-incubation either slowly or rapidly. The water content in the second period was maintained or adjusted slowly to 30–60 %. Cumulative respiration differed between water contents but was not consistently different between rapid and slow drying in the first period. We conclude that the response of microbial activity to a certain water content is influenced by the previous water content whereas the speed at which the water content is adjusted had little effect on respiration at target water content.     

Applicability of a sequential P fractionation procedure to Si in sediment

Purpose  

A sequential phosphorus (P) fractionation procedure for sediments was applied to silicon (Si) to test its applicability. We wanted to know (1) whether it would be used in a cost-efficient way to study the finding of both elements, defining Si pools corresponding to the respective P pools, and in particular, (2) whether it could be shown that redox-sensitive processes affect Si mobility in sediment.