Daniel B. Wiedemeier

Improved assessment of pyrogenic carbon quantity and quality in environmental samples by high-performance liquid chromatography

The analysis of pyrogenic carbon (PyC) in environmental samples is of great interest, e.g. for carbon cycle assessment, (bio-)char characterization and palaeo-environmental or archeological reconstruction. Here, an HPLC method (HPLC) is presented that reproducibly quantifies benzene polycarboxylic acids (BPCA) as molecular markers for PyC in various kinds of environmental samples. It operates at low pH without requiring an organic modifier and was thoroughly tested with PyC reference materials and a peatland core that served as a feasibility and plausibility check. Compared to the established gas chromatography (GC) method, the HPLC method results in higher BPCA quantification reproducibility by showing a significantly smaller coefficient of variation (HPLC: 5%, GC: 16-23%). It works well with small sample amounts, as for instance from sediment cores and aerosol collectors, and requires less sample preparation work than the GC method. Moreover, the here presented HPLC method facilitates (13)C and (14)C analyses on PyC from environmental samples.

Pyrogenic molecular markers: Linking PAH with BPCA analysis

Molecular characterization of pyrogenic organic matter (PyOM) is of great interest to understand the formation and behavior of these increasingly abundant materials in the environment. Two molecular marker methods have often been used to characterize and trace PyOM: polycyclic aromatic hydrocarbon (PAH) and benzenepolycarboxylic acid (BPCA) analysis. Since both methods target pyrogenic polycyclic compounds, we investigated the linkages between the two approaches using chars that were produced under controlled conditions. Rye and maize straws and their analogues charred at 300, 400 and 500 °C, respectively, were thus analyzed with both methods. Moreover, we also measured BPCAs directly on the lipid extracts, on which PAHs were analyzed, and on the respective extraction residues, too. Both methods revealed important features of the chars, in particular the increasing degree of aromatic condensation with increasing highest heating temperature (HTT). The overlap between the two methods was identified in the lipid fraction, where the proportion of benzenetricarboxylic acids (B3CAs) correlated with PAH abundance. The results confirmed the validity and complementarity of the two molecular marker methods, which will likely continue to play a crucial role in PyOM research due to the recent developments of compound-specific PAH and BPCA stable carbon (δ(13)C) and radiocarbon ((14)C) isotope methods.

Characterization, Quantification and Compound-specific Isotopic Analysis of Pyrogenic Carbon Using Benzene Polycarboxylic Acids (BPCA)

Fire-derived, pyrogenic carbon (PyC), sometimes called black carbon (BC), is the carbonaceous solid residue of biomass and fossil fuel combustion, such as char and soot. PyC is ubiquitous in the environment due to its long persistence, and its abundance might even increase with the projected increase in global wildfire activity and the continued burning of fossil fuel. PyC is also increasingly produced from the industrial pyrolysis of organic wastes, which yields charred soil amendments (biochar). Moreover, the emergence of nanotechnology may also result in the release of PyC-like compounds to the environment. It is thus a high priority to reliably detect, characterize and quantify these charred materials in order to investigate their environmental properties and to understand their role in the carbon cycle. Here, we present the benzene polycarboxylic acid (BPCA) method, which allows the simultaneous assessment of PyCs characteristics, quantity and isotopic composition (13C and 14C) on a molecular level. The method is applicable to a very wide range of environmental sample materials and detects PyC over a broad range of the combustion continuum, i.e., it is sensitive to slightly charred biomass as well as high temperature chars and soot. The BPCA protocol presented here is simple to employ, highly reproducible, as well as easily extendable and modifiable to specific requirements. It thus provides a versatile tool for the investigation of PyC in various disciplines, ranging from archeology and environmental forensics to biochar and carbon cycling research.

Decoupled sedimentary records of combustion: Causes and implications

Pyrogenic carbon (PyC) is a collective term for carbon-rich residues comprised of a continuum of products arising from biomass burning and fossil-fuel combustion. PyC is ubiquitous in the environment where it can be transported by wind and water before being deposited in aquatic sediments. We compare results from four different methods used to trace PyC that were applied to a high-temporal resolution sedimentary record in order to constrain changes in PyC concentrations and fluxes over the past ~250 years. We find markedly discordant records for different PyC tracers, particularly during the pre-industrial age, implying different origins and modes of supply of sedimentary PyC. In addition to providing new insights into the composition of sedimentary combustion products, this study reveals that elucidation of past combustion processes, and development of accurate budgets of PyC production and deposition on local to regional scales requires careful consideration of both source characteristics and transport processes.

Global-scale evidence for the refractory nature of riverine black carbon

Wildfires and incomplete combustion of fossil fuel produce large amounts of black carbon. Black carbon production and transport are essential components of the carbon cycle. Constraining estimates of black carbon exported from land to ocean is critical, given ongoing changes in land use and climate, which affect fire occurrence and black carbon dynamics. Here, we present an inventory of the concentration and radiocarbon content (∆14C) of particulate black carbon for 18 rivers around the globe. We find that particulate black carbon accounts for about 15.8 ± 0.9% of river particulate organic carbon, and that fluxes of particulate black carbon co-vary with river-suspended sediment, indicating that particulate black carbon export is primarily controlled by erosion. River particulate black carbon is not exclusively from modern sources but is also aged in intermediate terrestrial carbon pools in several high-latitude rivers, with ages of up to 17,000 14C years. The flux-weighted 14C average age of particulate black carbon exported to oceans is 3,700 ± 400 14C years. We estimate that the annual global flux of particulate black carbon to the ocean is 0.017 to 0.037 Pg, accounting for 4 to 32% of the annually produced black carbon. When buried in marine sediments, particulate black carbon is sequestered to form a long-term sink for CO2.Particulate black carbon in rivers can have ages of up to 17,000 14C years before it is sequestered in the oceans, according to an inventory of particulate black carbon in 18 rivers across the globe.

Five-Year Survival of Short Single-Tooth Implants (6 mm): A Randomized Controlled Clinical Trial:

The aim of the present study was to evaluate whether 6-mm dental implants in the posterior segments of either jaw perform equally well in terms of clinical and radiographic outcomes when compared with 10-mm implants after 5 y of loading. Patients with single-tooth gaps in the posterior area who were scheduled for implant therapy were randomly assigned to a group receiving either a 6- or 10-mm implant. After a healing period of 10 wk, implants were loaded with a screw-retained single crown and followed up at yearly intervals. Of 96 patients, 86 could be recalled after 5 y. The implant survival rates amounted to 91% (95% confidence interval: 0.836 to 0.998) for the 6-mm group and 100% for the 10-mm group (P = 0.036). Median crown-to-implant (C/I) ratios were 1.75 (interquartile range [IQR], 1.50 to 1.90) for the 6-mm group and 1.04 (IQR, 0.95 to 1.15) for the 10-mm group, whereas the median marginal bone levels measured −0.29 mm (IQR, −0.92 to 0.23) for the 6-mm group and −0.15 mm (IQR: −0.93 – 0.41) for the 10-mm group after 5 y. The C/I ratio turned out to be statistically significant (P < 0.001), whereas marginal bone levels showed no significant difference between the groups. The 6-mm implants exhibited significantly lower survival rates than the 10-mm implants over 5 y, whereas there was no difference between upper and lower jaws in terms of survival (P = 0.58). Lost implants did not show any sign of marginal bone loss or peri-implant infection previous to loss of osseointegration. High C/I ratio and implant length had no significant effect on marginal bone level changes or technical and biological complications (German Clinical Trials Registry: DRKS00006290).

Location of unaccessible implant surface areas during debridement in simulated peri-implantitis therapy

BackgroundAn in vitro model for peri-implantitis treatment was used to identify areas that are clinically difficult to clean by analyzing the pattern of residual stain after debridement with commonly employed instruments.MethodsOriginal data from two previous publications, which simulated surgical (SA) and non-surgical (NSA) implant debridement on two different implant systems respectively, were reanalyzed regarding the localization pattern of residual stains after instrumentation. Two blinded examiners evaluated standardized photographs of 360 initially ink-stained dental implants, which were cleaned at variable defect angulations (30, 60, or 90°), using different instrument types (Gracey curette, ultrasonic scaler or air powder abrasive device) and treatment approaches (SA or NSA). Predefined implant surface areas were graded for residual stain using scores ranging from one (stain-covered) to six (clean). Score differences between respective implant areas were tested for significance by pairwise comparisons using Wilcoxon-rank-sum-tests with a significance level α = 5%.ResultsBest scores were found at the machined surface areas (SA: 5.58 ± 0.43, NSA: 4.76 ± 1.09), followed by the tips of the threads (SA: 4.29 ± 0.44, NSA: 4.43 ± 0.61), and areas between threads (SA: 3.79 ± 0.89, NSA: 2.42 ± 1.11). Apically facing threads were most difficult to clean (SA: 1.70 ± 0.92, NSA: 2.42 ± 1.11). Here, air powder abrasives provided the best results.ConclusionMachined surfaces at the implant shoulder were well accessible and showed least amounts of residual stain. Apically facing thread surfaces constituted the area with most residual stain regardless of treatment approach.

Comparison of Profilometric and Microindentation Analyses for Determining the Impact of Saliva on the Abrasion of Initially Eroded Enamel

The aim of this in vitro study was to investigate the impact of saliva on the abrasion of eroded enamel using two measuring methods. A total of 80 bovine enamel specimens from 20 bovine incisors were allocated to four experimental groups (n = 20 specimens per group). After baseline surface microhardness (SMH) measurements and profilometry all specimens were subjected to erosion (2 min, 1% citric acid, pH: 3.6, 37°C). SMH was determined again, and the depths of the Knoop indentations were calculated. Thereafter, specimens were incubated in human saliva (group 1 – no incubation/control, group 2 – 0.5 h, group 3 – 1 h, group 4 – 2 h) before toothbrush abrasion was performed. After final SMH measurements and profilometry, indentations were remeasured, and surface loss was calculated. SMH did not return to baseline values regardless of the length of saliva incubation. Further, an irreversible substance loss was observed for all specimens. With the indentation method, significantly (p < 0.05) more substance loss was found for controls (least square means ± standard error of 198 ± 19 nm) than for groups 2–4 (110 ± 10, 114 ± 11, and 105 ± 14 nm). Profilometric assessment showed significantly more substance loss for controls (122 ± 8 nm) than for group 4 (106 ± 5 nm). Intraclass correlation for interrater reliability between measurement methods was low (0.21, CI: 0.1–0.3), indicating poor agreement. Exposure of eroded enamel to saliva for up to 2 h could not re-establish the original SMH. The amount of measured substance loss depended on the measurement method applied.

Temperature-dependent erosivity of drinks in a model simulating oral fluid dynamics

OBJECTIVES Aim of this investigation was to study the temperature-dependent in vitro enamel erosion of five acidic drinks and citric acid under controlled conditions in an artificial mouth. METHODS The erosive potential of Orange juice, Coca-Cola Zero, Sprite Zero, two fruit teas and citric acid (control) was investigated on bovine enamel specimens at temperatures between 5 °C and 55 °C. The pH values and total calcium content of all test drinks were determined. Specimens were immersed into an artificial mouth to imitate physiological oral conditions for 60 h. Cyclic de- and re-mineralization was performed, imitating the intake of six drinks in six h followed by a six-hour remineralization phase, where only artificial saliva ran over the specimens. Total erosive enamel loss was determined by contact profilometry. Differences in substance loss at different temperatures were tested for statistical significance (p-values ≤ 0.05) by means of ANOVA. RESULTS Rising liquid temperature did not result in a considerable change of pH. Highest substance loss was observed for citric acid (33.6 ± 6 μm to 38.7 ± 6 μm), while only little erosion was induced by fruit tea (0.8 ± 1 μm to 5.9 ± 1 μm). Rising liquid temperature did not result in significantly increased substance loss for citric acid, orange juice and Coca-Cola Zero. Sprite Zero and both fruit teas, however, caused significantly (p < 0.001) more enamel loss at elevated temperature. CONCLUSIONS Not all investigated drinks showed a temperature-induced change in erosivity. CLINICAL SIGNIFICANCE For some erosive beverages it can be recommended to keep the consummation temperature as low as possible to decrease the risk of erosive tooth substance loss.

Use of a monopolar microneedle device in a transconjunctival, retroseptal approach

Transconjunctival approach is a standard procedure to address fractures of orbit and the infraorbital rim. Modifications such as transcaruncular or lateral canthal widening allow for extended orbital wall exposure. Especially concerning aesthetics, the transconjunctival approach shows benefits compared to the transcutaneous incisions, such as the transciliary and infraorbital access. Moreover, transconjunctival approach is favored in the literature concerning lid retraction. Monopolar devices have become popular in surgery in the past decades because of good depth control and simultaneous hemostasis with consequently improved overview. Also numerous surgeons use monopolar device in orbital surgery, their safety have never been proved. In this study monopolar microneedle device is compared with conventional access by scalpel concerning lid retraction, foreign body sensation and formation of symblepharon. In our collective complication rates were comparable between the scalpel and the microneedle group. The monopolar microneedle device shows favorable results compared with the scalpel and is easy to handle. Weather the conventional access by scalpel or the access by monopolar device is selected, is rather driven by the surgeons preferences than by statistical relevance. Nevertheless, monopolar microneedle device shows better depth control and simplifies readaptation of the conjunctival wounds margin.