Atmospheric Concentrations and Potential Sources of Dioxin-Like Contaminants to Acadia National Park.

Acadia National Park (ANP) is located on Mt. Desert Island, ME on the U.S. Atlantic coast. ANP is routinely a top-ten most popular National Park with over four million visits in 2022. The overall contribution and negative effects of long-range atmospheric transport and local sources of dioxin-like contaminants endangering natural and wildlife resources is unknown. Dioxin-like (DL) contaminants polychlorinated dibenzo-p-dioxins (∑PCDD) and polychlorinated dibenzofurans (∑PCDF), non-ortho coplanar PCBs (∑CP4), and polychlorinated naphthalenes (∑PCNs) were measured at the McFarland Hill air monitoring station (44.37°N, 68.26°W). On a mass/volume basis, total PCNs averaged 90.9 % (788 fg/m3) of DL contaminants measured annually, with 92.9 % of the collected total in the vapor-phase. Alternatively, total dioxin/furans (∑PCDD/Fs) represented 71.6 % of the total toxic equivalence (∑TEQ) (1.018 fg-TEQ/m3), with 69.7 % in the particulate-phase. Maximum concentrations measured for individual sampling events for ∑PCDD/F, ∑CP4, and ∑PCN were 159 (winter), 139 (summer), and 2100 (autumn), fg/m3 respectively. Whereas the maximum ∑TEQ concentrations for individual sampling events for ∑PCDD/F, ∑CP4, and ∑PCN were 2.8 (autumn), 0.38 (summer), and 0.71 (autumn), fg-TEQ/m3 respectively. Pearson correlations were calculated for ∑PCDD/Fs and ∑PCN particulate/vapor-phase air concentrations and PM2.5 wood smoke "indicator" species. The most significant correlations were observed in autumn for particulate-phase ∑PCDD/Fs suggesting a relationship between visitation-generated combustion sources (campfires and/or waste burning) or climate-change mediated forest fires. Significant Clausius-Clapeyron (C-C) correlations observed for particulate-phase ∑PCDDs (r2=0.567) as ambient temperatures decreased suggests a connection between localized domestic heating sources or visitor-based burning of wood/trash resources. Alternatively, highly significant C-C vapor-phase ∑CP4-PCBs correlations (r2=0.815) implies that the majority of ∑CP4-PCB loading to ANP is from long-range atmospheric transport processes. Based on these findings, Acadia National Park should be classified as a remote site with minor depositional impacts from ∑PCDD/Fs, ∑CP4-PCBs, and ∑PCN atmospheric transport or local diffuse sources.

Temporal Trends of Great Lakes Legacy Contaminants: Ecological and Biological Considerations Applying the Age-Trend Model.

The USEPA Great Lakes Fish Monitoring and Surveillance Program (GLFMSP) has been monitoring top predator lake trout and walleye contaminant concentrations since the early 1970s. Our research revealed that select legacy contaminant groups (∑PCBs, ∑DDTs, ∑chlordanes, and ∑5PBDEs) have similar t1/2 and k2 values across the Great Lakes, with the exception of both Lake Erie sites and the Lake Superior─Keweenaw Point site. The slower halving times determined at both Lake Erie sites are consistent with legacy contaminant remobilization due to extreme weather climate effects and past remedial actions on the Detroit River, whereas the Lake Superior─Keweenaw Point site demonstrates contaminant halving times approaching the exponential minimum. Overall, Great Lakes select contaminant groupings have decreased between 25.8 and 97.9% since 2004. An age-normalized Great Lakes Contaminant Index (GLCI) was devised, indicating both Lake Michigan sites as the most highly impacted. The mean absolute deviation statistic was applied, documenting the need to age-correct contaminant trends due to highly variable age profiles. With the noted exceptions, the uniformity of age-corrected trend modeling suggests that a combination of the fundamental biological and physicochemical mechanisms of natural contaminant sequestration, declining dissolved water concentrations, accumulation/metabolism/depuration, and the overall reduction of legacy contaminant loading are driving the generally consistent rates of declines in the Great Lakes. Many of the biological and ecological stressors currently associated with climate change appear to be accounted for by the age-trend model.

The fundamental thermodynamic bounds on finite models.

The minimum heat cost of computation is subject to bounds arising from Landauer's principle. Here, I derive bounds on finite modeling-the production or anticipation of patterns (time-series data)-by devices that model the pattern in a piecewise manner and are equipped with a finite amount of memory. When producing a pattern, I show that the minimum dissipation is proportional to the information in the model's memory about the pattern's history that never manifests in the device's future behavior and must be expunged from memory. I provide a general construction of a model that allows this dissipation to be reduced to zero. By also considering devices that consume or effect arbitrary changes on a pattern, I discuss how these finite models can form an information reservoir framework consistent with the second law of thermodynamics.

Polychlorinated Naphthalenes across the Great Lakes: Lake Trout and Walleye Concentrations, Trends, and TEQ Assessment-2004-2018.

Polychlorinated naphthalenes (PCNs) were measured in lake trout and walleye over the period 2004-2018, utilizing isotope dilution techniques with high-resolution gas chromatography/high-resolution mass spectrometry to assess concentrations and toxic equivalence (TEQ). An age-trend model was applied to mitigate the effect of a changing lake trout age structure. Most Great Lakes Fish Monitoring and Surveillance Program sampling sites demonstrated significant half-life and percent decreases for lake trout total PCNs and total TEQ over the 2004-2018 period, the exceptions being Lake Erie lake trout and walleye which illustrated increasing concentrations. Great Lakes total PCN concentrations ranged between 5701 and 100 pg/g ww, whereas total PCN TEQ concentrations ranged between 8.89 and 0.13 pg-TEQ/g ww. Based on the average number of chlorines per naphthalene, we determined that the overall lake trout and walleye PCN congener distribution has significantly shifted to a lower-chlorinated composition in the Great Lakes (5.33 to 4.48 Cl/CN) and has resulted in a substantial 59.1% reduction of the overall total PCN TEQ burden. A prominent PCN concentration trend breakpoint was observed in Lake Ontario lake trout over the 2012-2016 period likely associated with hazardous waste cleanups, channel dredging, and spoils disposal in the Detroit River and western-basin of Lake Erie.

Concentrations, toxic equivalence, and age-corrected trends of legacy organic contaminants in Lake Champlain lake trout: 2012-2018.

Our study is the first comprehensive, multi-year assessment of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), organochlorine pesticides (OCPs), polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDD/Fs) lake trout concentrations and trends in Lake Champlain (LC). Lake trout whole-fish, fillets, and eggs were collected over the 2012-2018 study period. Total PCB concentrations (395.7 ng/g wet weight (ww)) were the highest average concentration of any contaminant grouping reported in this study. Whole-fish lake trout modeling revealed highly significant (p < 0.05) log-linear correlations for all dioxin-like contaminants measured. Overall contaminant decreases for the 2012-2018 period ranged from 20.9% (total PCNs) to 39.3% (2378-TCDD). Contaminant decreases for total PCBs and total-5-PBDEs were 30.9% and 48.3%, respectively. Of particular significance were the measured total PBDE concentrations (74.3 ng/g ww) found in LC whole-fish lake trout. Log-linear forecasting indicates that whole-fish lake trout TEQs will be below the guidelines protective of wildlife thresholds during the periods 2035-2047 (TRGbird) and 2062-2088 (TRGmammal). Based on current USEPA guidelines, all lake trout fillets from Lake Champlain analyzed for this study exceed the human health cancer screening value of 0.15 pg-TEQ/g ww by a substantial margin (average = 8.61 pg-TEQ/g ww). Dioxin-like trend data collected for Lake Champlain indicates that the mechanisms of contaminant uptake, trends, and yearly percent decline reflect those found in the Great Lakes.

Extreme Dimensionality Reduction with Quantum Modeling.

Effective and efficient forecasting relies on identification of the relevant information contained in past observations-the predictive features-and isolating it from the rest. When the future of a process bears a strong dependence on its behavior far into the past, there are many such features to store, necessitating complex models with extensive memories. Here, we highlight a family of stochastic processes whose minimal classical models must devote unboundedly many bits to tracking the past. For this family, we identify quantum models of equal accuracy that can store all relevant information within a single two-dimensional quantum system (qubit). This represents the ultimate limit of quantum compression and highlights an immense practical advantage of quantum technologies for the forecasting and simulation of complex systems.

Trends of polychlorinated dioxins, polychlorinated furans, and dioxin-like polychlorinated biphenyls in Chinook and Coho salmonid eggs from a Great Lakes tributary.

Eggs from mature Chinook (Oncorhynchus tshawytscha) and Coho (Oncorhynchus kisutch) salmon were collected between 2004 and 2014 from the Salmon River fish hatchery in Altmar, New York. The egg samples were analyzed for seventeen polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), as well as four dioxin-like polychlorinated biphenyls (DL-PCBs) using USEPA methods 1613 and 1668. Salmonid eggs were chosen as a tissue of interest since salmon feed at all trophic levels of the food web as they grow, and spawn in a narrow range of ages providing consistent, representative, and temporal samples of contaminant exposure. First-order decay models indicate decreasing trends for all select contaminants in both species, expressed by a toxic equivalence (TEQ) half-life (t1/2) of 11 years in Chinook and Coho eggs. No significant statistical difference in contaminant elimination rates were noted between species. TEQ elimination rates for Coho and Chinook eggs were not significantly different (p > 0.05) when compared with published Lake Ontario whole-fish lake trout elimination rates. Our research demonstrates that salmonid eggs are an effective means to assess PCDD, PCDF, and DL-PCB exposures and long-term trends in the Great Lakes.

Maximum one-shot dissipated work from Rényi divergences.

Thermodynamics describes large-scale, slowly evolving systems. Two modern approaches generalize thermodynamics: fluctuation theorems, which concern finite-time nonequilibrium processes, and one-shot statistical mechanics, which concerns small scales and finite numbers of trials. Combining these approaches, we calculate a one-shot analog of the average dissipated work defined in fluctuation contexts: the cost of performing a protocol in finite time instead of quasistatically. The average dissipated work has been shown to be proportional to a relative entropy between phase-space densities, to a relative entropy between quantum states, and to a relative entropy between probability distributions over possible values of work. We derive one-shot analogs of all three equations, demonstrating that the order-infinity Rényi divergence is proportional to the maximum possible dissipated work in each case. These one-shot analogs of fluctuation-theorem results contribute to the unification of these two toolkits for small-scale, nonequilibrium statistical physics.

Age-Corrected Trends and Toxic Equivalence of PCDD/F and CP-PCBs in Lake Trout and Walleye from the Great Lakes: 2004-2014.

Our research reports polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (CP-PCBs) concentrations and age-corrected trends for lake trout and walleye in the Great Lakes over the 2004-2014 period. We determined that age-contaminant corrections are required to accurately report contaminant trends due to significant lake trout age structure changes. The age-trend model (ATM) described here uses a lake-specific age-contaminant regression to mitigate the effect of a fluctuating lake trout age structure to directly improve the log-linear regression model. ATM results indicate that half-life (t1/2) and percent decreases for PCDD/Fs, CP-PCBs, and toxic equivalence (TEQ) (average -56 to 70%) were fairly uniform and consistent across the Great Lakes over the 2004-2014 period. The vast majority of TEQ associated with all Great Lakes lake trout and walleye samples is due to the nonortho CP-PCBs (average = 79%) as compared with PCDD/Fs (average = 21%). On average, CP-PCB_126 individually accounted for over 95% of the total CP-PCB TEQ. A retrospective analysis (1977-2014) of 2378-TCDF and 2378-TCDD raw concentrations in Lake Ontario lake trout revealed decreases of 94% and 96%, respectively. Tissue residue guidelines for wildlife protection based on lake trout and walleye total TEQ were uniformly exceeded in all the Great Lakes.

Thermodynamics of complexity and pattern manipulation.

Many organisms capitalize on their ability to predict the environment to maximize available free energy and reinvest this energy to create new complex structures. This functionality relies on the manipulation of patterns-temporally ordered sequences of data. Here, we propose a framework to describe pattern manipulators-devices that convert thermodynamic work to patterns or vice versa-and use them to build a "pattern engine" that facilitates a thermodynamic cycle of pattern creation and consumption. We show that the least heat dissipation is achieved by the provably simplest devices, the ones that exhibit desired operational behavior while maintaining the least internal memory. We derive the ultimate limits of this heat dissipation and show that it is generally nonzero and connected with the pattern's intrinsic crypticity-a complexity theoretic quantity that captures the puzzling difference between the amount of information the pattern's past behavior reveals about its future and the amount one needs to communicate about this past to optimally predict the future.

The complex and quaternionic quantum bit from relativity of simultaneity on an interferometer.

The patterns of fringes produced by an interferometer have long been important testbeds for our best contemporary theories of physics. Historically, interference has been used to contrast quantum mechanics with classical physics, but recently experiments have been performed that test quantum theory against even more exotic alternatives. A physically motivated family of theories are those where the state space of a two-level system is given by a sphere of arbitrary dimension. This includes classical bits, and real, complex and quaternionic quantum theory. In this paper, we consider relativity of simultaneity (i.e. that observers may disagree about the order of events at different locations) as applied to a two-armed interferometer, and show that this forbids most interference phenomena more complicated than those of complex quantum theory. If interference must depend on some relational property of the setting (such as path difference), then relativity of simultaneity will limit state spaces to standard complex quantum theory, or a subspace thereof. If this relational assumption is relaxed, we find one additional theory compatible with relativity of simultaneity: quaternionic quantum theory. Our results have consequences for current laboratory interference experiments: they have to be designed carefully to avoid rendering beyond-quantum effects invisible by relativity of simultaneity.

Guaranteed energy-efficient bit reset in finite time.

Landauer's principle states that it costs at least kBTln2 of work to reset one bit in the presence of a heat bath at temperature T. The bound of kBTln2 is achieved in the unphysical infinite-time limit. Here we ask what is possible if one is restricted to finite-time protocols. We prove analytically that it is possible to reset a bit with a work cost close to kBTln2 in a finite time. We construct an explicit protocol that achieves this, which involves thermalizing and changing the system's Hamiltonian so as to avoid quantum coherences. Using concepts and techniques pertaining to single-shot statistical mechanics, we furthermore prove that the heat dissipated is exponentially close to the minimal amount possible not just on average, but guaranteed with high confidence in every run. Moreover, we exploit the protocol to design a quantum heat engine that works near the Carnot efficiency in finite time.

The uncertainty principle enables non-classical dynamics in an interferometer.

The quantum uncertainty principle stipulates that when one observable is predictable there must be some other observables that are unpredictable. The principle is viewed as holding the key to many quantum phenomena and understanding it deeper is of great interest in the study of the foundations of quantum theory. Here we show that apart from being restrictive, the principle also plays a positive role as the enabler of non-classical dynamics in an interferometer. First we note that instantaneous action at a distance should not be possible. We show that for general probabilistic theories this heavily curtails the non-classical dynamics. We prove that there is a trade-off with the uncertainty principle that allows theories to evade this restriction. On one extreme, non-classical theories with maximal certainty have their non-classical dynamics absolutely restricted to only the identity operation. On the other extreme, quantum theory minimizes certainty in return for maximal non-classical dynamics.